Modified resins and uses thereof

ABSTRACT

Modified thermoplastic hydrocarbon thermoplastic resins are provided, as well as methods of their manufacture and uses thereof in rubber compositions. The modified thermoplastic resins are modified by decreasing the relative quantity of the dimer, trimer, tetramer, and pentamer oligomers as compared to the corresponding unmodified thermoplastic resin polymers, resulting in a product that exhibits a greater shift in the glass transition temperature of the elastomer(s) used in tire formulations. This translates to better viscoelastic predictors of tire tread performance, such as wet grip and rolling resistance. The modified thermoplastic resins impart remarkable properties on various rubber compositions, such as tires, belts, hoses, brakes, and the like. Automobile tires incorporating the modified thermoplastic resins are shown to possess excellent results in balancing the properties of rolling resistance, tire wear, snow performance, and wet braking performance.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation application of U.S. patentapplication Ser. No. 15/944,502, filed Apr. 3, 2018 (published asUS2018/0282444A1) which, in turn, is a continuation application ofinternational patent application PCT/US2018/025755, filed Apr. 2, 2018which designates the United States and claims priority from U.S.Provisional Application No. 62/480,894, filed Apr. 3, 2017. The presentcontinuation application claims priority to each of the aboveapplications and incorporates herein the entire contents thereof byreference.

PARTIES TO A JOINT RESEARCH AGREEMENT

This disclosure was created pursuant to a joint development agreementbetween Eastman Chemical Company, a Delaware corporation, andContinental Reifen Deutschland GmbH, a German corporation, that ineffect on or before the date the claimed invention was made, and theclaimed invention was made as a result of activities undertaken withinthe scope of the joint development agreement.

FIELD

Modified thermoplastic resins are disclosed in which the fraction ofoligomer is reduced, where oligomers are defined as dimer, trimer,tetramer, and/or pentamer species of monomers used to produce themodified thermoplastic resin. The low oligomer content of the modifiedthermoplastic resins provides a higher glass transition temperature (Tg)to z-average molecular weight (Mz) ratio (Tg/Mz) than is currentlyavailable with corresponding unmodified commercial thermoplastic resins.The modified thermoplastic resins can improve the performance propertiesof the rubber and elastomer compositions and cured rubber and elastomercompounds. Further, methods of preparing the modified thermoplasticresins are disclosed. Various uses and end products that impartexcellent performance due to the unexpected properties of these modifiedthermoplastic resins are also disclosed.

BACKGROUND

Hydrocarbon and natural thermoplastic resins can be used to modify theviscoelastic properties of rubber compositions, such as those used inthe manufacture of rubber-based products, including tire treadcompounds, such that tire tread performance properties (such as wetgrip, rolling resistance) are enhanced. Resins can also be used asprocessing aids to reduce the compound viscosity, and they can providean improvement in tack which is needed for the tire constructionprocess.

Resins are increasingly used in rubber mixtures for vehicle tireapplications, in particular in rubber mixtures for tire treads. U.S.Patent Application Publication No. 2016/0222197 discloses tire treadscontaining thermoplastic resins in amounts exceeding 50 phr. A goodcompatibility between rubber and thermoplastic resin is a prerequisitefor achieving high thermoplastic resin loadings in the polymer matrix.

Current thermoplastic resin technology for tires uses high glasstransition thermoplastic resins to modify the rubber glass transitiontemperature Tg and viscoelastic properties to improve wet grip androlling resistance performance balance. The wet grip performance must bebalanced with other tire properties including rolling resistance andwear that are affected by the introduction of thermoplastic resin.

Hydrocarbon thermoplastic resins are added to an internal mixer alongwith elastomers, reinforcing particulate fillers, and other ingredientsto form the rubber compounds used in the construction of automobiletires. The formation of a single-phase blend of thermoplastic resin andelastomer is critical to the effectiveness of the thermoplastic resin tomodify the viscoelastic properties of the elastomer. One use case ofthermoplastic resins in tire tread applications is to increase the glasstransition temperature (Tg) of the elastomer compound such that there ishigher hysteretic energy loss for the mechanism of improved tire wetgrip performance. However, this increase in hysteresis for wet grip mustbe balanced by the need for low hysteresis compound properties atelevated temperatures in order to achieve low rolling resistance (fuelefficient) tires.

The ability of a thermoplastic resin to effectively balance the wet gripand rolling resistance performance requirements in this way depends onthe thermoplastic resin glass transition temperature (Tg), numberaverage molecular weight (Mn), and molecular weight distribution. The Tgof typical hydrocarbon thermoplastic resins have a strong dependence onmolecular weight, Mn. Low Tg thermoplastic resins have low Mn, whileincreasing Mn increases the thermoplastic resin Tg. In a typicalthermoplastic resin molecular weight distribution, the low molecularweight thermoplastic resin species are not efficient for modifying theelastomer Tg because they have lower glass transition temperatures.Additionally, the very high molecular weight thermoplastic resin species(characterized by the z-average molecular weight, Mz) are not efficienteither because they are not compatible with the elastomers. The currentmethod to increase the thermoplastic resin Tg is by increasing themolecular weight; however, this is not efficient because during typicalpolymerization conditions, the amount of incompatible high molecularweight thermoplastic resin increases with increasing Mn.

It is therefore desirable to obtain a modified thermoplastic resin inwhich the modified thermoplastic resin has a high Tg while maintaining alow Mz to most efficiently modify the elastomer compound Tg whilemaintaining compatibility with the rubber matrix.

SUMMARY

Provided herein are modified thermoplastic resin compositions. It hasbeen discovered that modification of thermoplastic resins by reducingthe relative amount of oligomer present in the modified thermoplasticresin as compared to a corresponding unmodified thermoplastic resin,where oligomers are defined as dimer, trimer, tetramer, and/or pentamerspecies of monomers used to produce the modified thermoplastic resinprovides a higher glass transition temperature (Tg) to z-averagemolecular weight (Mz) ratio (Tg/Mz) than is currently available withcorresponding unmodified commercial thermoplastic resins. Themodification of thermoplastic resins according to the methods disclosedherein confers superior unexpected properties to products incorporatingsuch modified thermoplastic resins, such that products, such as rubberproducts, adhesive, molded plastics, tires, belts, gaskets, hoses, andthe like, possess superior properties as compared to similar productswithout the disclosed modified thermoplastic resins. Disclosed are alsomethods of obtaining, manufacturing, or creating such modifiedthermoplastic resins, as well as various products incorporating thedisclosed modified thermoplastic resins.

Thus, in one embodiment, disclosed are modified thermoplastic resinsprepared by polymerization of one or more monomers and having a glasstransition temperature (Tg) of between −50° C. and 160° C., a numberaverage molecular weight of less than 3,000 g/mol, a z-average molecularweight (Mz) of less than 9,000 g/mol, comprising less than or equal to55 wt % oligomers by gel permeation chromatography (GPC), or less thanor equal to 38 wt % by high resolution thermogravimetric analysis (TGA),and where oligomers consist of dimers, trimers, tetramers, pentamers, ora mixture thereof, of the one or more monomers.

In such embodiments, the glass transition temperature (Tg) is between−50° C. and 160° C., the number average molecular weight is less than1,000 g/mol, and/or the z-average molecular weight is less than 9,500g/mol. Alternatively, the Tg is between 0° C. and 140° C., the numberaverage molecular weight is less than 850 g/mol, and/or the z-averagemolecular weight is less than 8,000 g/mol.

Additionally, such modified thermoplastic resins are obtained bymodification of pure monomer thermoplastic resin (PMR), C5 thermoplasticresin, C5/C9 thermoplastic resin, C9 thermoplastic resin, terpenethermoplastic resin, indene-coumarone (IC) thermoplastic resin,dicyclopentadiene (DCPD) thermoplastic resin, hydrogenated or partiallyhydrogenated pure monomer (PMR) thermoplastic resin, hydrogenated orpartially hydrogenated C5 thermoplastic resin, hydrogenated or partiallyhydrogenated C5/C9 thermoplastic resin, hydrogenated or partiallyhydrogenated C9 thermoplastic resin, hydrogenated or partiallyhydrogenated dicyclopentadiene (DCPD) thermoplastic resin, terpenethermoplastic resin, modified indene-coumarone (IC) thermoplastic resin,or a mixture thereof.

In another embodiment, the modified thermoplastic resins describedherein have a glass transition temperature (Tg) of between −50° C. and160° C., between 0° C. and 140° C., or between 20° C. and 120° C.,and/or a number average molecular weight (Mn) of the modifiedthermoplastic resin is less than or equal to 1,000 g/mol, 500 g/mol, or250 g/mol, and/or wherein the z-average molecular weight (Mz) is lessthan or equal to 9,000 g/mol, 8,000 g/mol, or 6,000 g/mol.

In such embodiments, the high resolution TGA analysis is conducted witha thermal gravimetric analyzer calibrated by curie point of magnetictransition standards according to ASTM method E1582, procedure C; and/orwherein the high resolution TGA analysis is conducted using a TAInstruments Q500 thermal gravimetric analyzer with sensitivity set to2.0 and resolution set to 3.0 by heating the modified thermoplasticresin in nitrogen with a scanning rate of 20 degrees per minute fromambient temperature to 625° C., and/or the GPC analysis is conducted at30° C. in tetrahydrofuran solvent at a flow rate of 1 ml/min with a GPCinstrument comprising a refractive index detector, a highly cross-linkedpolystyrene-divinylbenzene gel column, and/or a column comprisingpolymer particles with a nominal particle size of 6 μm.

In other embodiments, the modified thermoplastic resins described hereinpossesses the properties of formula I:

$\begin{matrix}{S = {\left( \frac{T_{g}}{M_{z}} \right){\text{/}\left\lbrack {{Oligomer} \times \left( {1 - \frac{T_{10}}{T_{\max}}} \right)} \right\rbrack}}} & I\end{matrix}$

In such embodiments, the Tg is the glass transition temperature indegrees Celsius of the modified thermoplastic resin, Mz is the z-averagemolecular weight of the modified thermoplastic resin, Oligomer is thefraction of oligomer present in the modified thermoplastic resin asmeasured by high resolution thermal gravimetric analysis (TGA) or gelpermeation chromatography (GPC), T₁₀ is the temperature at which themodified thermoplastic resin loses about 10% of its weight as measuredby high resolution TGA, and T_(max) is the temperature of the maximumfirst derivative value of the modified thermoplastic resin as measuredby high resolution TGA. In such embodiments, the value of S is greaterthan or equal to 2 and less than 50,000 when Oligomer is determined byGPC, or greater than or equal to 5 and less than 10,000 when Oligomer isdetermined by high resolution TGA and the value of Mz is less than orequal to 9,000 g/mol.

In another embodiment of the thermoplastic resins described by FormulaI, the resins possess one or more of the following properties: a glasstransition temperature (Tg) of between −50° C. and 160° C., a numberaverage molecular weight of less than 1,000 g/mol, and/or a z-averagemolecular weight of less than 9,500 g/mol. Alternatively, in suchembodiments, the modified thermoplastic resins described herein possessone or more of the following properties: a Tg of between 0° C. and 140°C., a number average molecular weight of less than 850 g/mol, and/or az-average molecular weight of less than 8,000 g/mol.

Such embodiments of the modified thermoplastic resins described byFormula I are obtained by modification of pure monomer thermoplasticresin (PMR), C5 thermoplastic resin, C5/C9 thermoplastic resin, C9thermoplastic resin, terpene thermoplastic resin, indene-coumarone (IC)thermoplastic resin, dicyclopentadiene (DCPD) thermoplastic resin,hydrogenated or partially hydrogenated pure monomer (PMR) thermoplasticresin, hydrogenated or partially hydrogenated C5 thermoplastic resin,hydrogenated or partially hydrogenated C5/C9 thermoplastic resin,hydrogenated or partially hydrogenated C9 thermoplastic resin,hydrogenated or partially hydrogenated dicyclopentadiene (DCPD)thermoplastic resin, terpene thermoplastic resin, modifiedindene-coumarone (IC) thermoplastic resin, or a mixture thereof.

In other embodiments where the modified thermoplastic resins aredescribed by Formula I, and the oligomer content is determined by highresolution TGA, the modified thermoplastic resins possess one or more ofthe following properties: (a) the modified thermoplastic resin is a PMRresin, where the value of Tg/Mz is greater than or equal to 0.14, and:the weight percent of oligomer is less than 17, and/or the value ofT₁₀/T_(max) is greater than or equal to 0.90, and/or the value of S isgreater than 17; (b) the modified thermoplastic resin is C5 resin, and:the weight percent of oligomer is less than 14, and/or the value ofT₁₀/T_(max) is greater than or equal to 0.92, and/or the value of S isgreater than or equal to 5; (c) the modified thermoplastic resin is aC5/C9 resin, and: the weight percent of oligomer is less than 15, and/orthe value of T₁₀/T_(max) is greater than or equal to 0.92, and/or thevalue of S is greater than or equal to 10; (d) the modifiedthermoplastic resin is a C9 resin, where the value of Tg/Mz is greaterthan or equal to 0.12, and: the weight percent of oligomer is less thanor equal to 15, and/or the value of T₁₀/T_(max) is greater than or equalto 0.88, and/or the value of S is greater than or equal to 16; (e) themodified thermoplastic resin is a hydrogenated or partially hydrogenatedDCPD resin, where the value of Tg/Mz is greater than 0.25, and theweight percent of oligomer is less than 31, and/or the value ofT₁₀/T_(max) is greater than 0.85, and/or the value of S is greater thanor equal to 10; (f) the modified thermoplastic resin is a hydrogenatedor partially hydrogenated PMR resin, where the value of Tg/Mz is greaterthan or equal to 0.30, and: the weight percent of oligomer is less thanor equal to 16, and/or the value of T₁₀/T_(max) is greater than 0.85,and/or the value of S is greater than or equal to 22; (g) the modifiedthermoplastic resin is a hydrogenated or partially hydrogenated PMRresin, where the value of Tg/Mz is less than 0.30, and: the weightpercent of oligomer is less than 38, and/or the value of T₁₀/T_(max) isgreater than 0.75, and/or the value of S is greater than or equal to 5;(h) the modified thermoplastic resin is a hydrogenated or partiallyhydrogenated C5 resin or a hydrogenated or partially hydrogenated C5/C9resin, and: the weight percent of oligomer is less than 30, and/or thevalue of T₁₀/T_(max) is greater than or equal to 0.90, and/or the valueof S is greater than or equal to 10; and/or (i) the modifiedthermoplastic resin is hydrogenated or partially hydrogenated C9, wherethe value of Tg/Mz is greater than or equal to 0.19, and: the weightpercent of oligomer is less than or equal to 13, and/or the value ofT₁₀/T_(max) is greater than 0.90, and/or the value of S is greater thanor equal to 16.

In other embodiments where the modified thermoplastic resins aredescribed by Formula I, and the oligomer content is determined by GPC,the modified thermoplastic resins possess one or more of the followingproperties: (a) the modified thermoplastic resin is a PMR resin, thevalue of Tg/Mz is greater than or equal to 0.14 K/(g/mol), the Oligomerhaving a molecular weight of less than 300 g/mol is less than or equalto 0.02, and the Oligomer having a molecular weight of less than 600g/mol is less than or equal to 0.1; (b) the modified thermoplastic resinis a C5 resin, and wherein: the Oligomer having a molecular weight ofless than 300 g/mol is less than 0.03, or the Oligomer having amolecular weight of less than 600 g/mol is less than 0.17; (c) themodified thermoplastic resin is a C5/C9 resin, and wherein: the Oligomerhaving a molecular weight of less than 300 g/mol is less than 0.03, orthe Oligomer having a molecular weight of less than 600 g/mol is lessthan 0.17; (d) the modified thermoplastic resin is a C9 resin, the valueof Tg/Mz is greater than or equal to 0.09 K/(g/mol), the Oligomer havinga molecular weight of less than 300 g/mol is less than or equal to 0.05,and the Oligomer having a molecular weight of less than 600 g/mol isless than 0.25; (e) the modified thermoplastic resin is a hydrogenatedor partially hydrogenated DCPD resin, the value of Tg/Mz is greater thanor equal to 0.25 K/(g/mol), and wherein: the Oligomer having a molecularweight of less than 300 g/mol is less than 0.16, or the Oligomer havinga molecular weight of less than 600 g/mol is less than 0.55; (f) themodified thermoplastic resin is a hydrogenated or partially hydrogenatedC5 resin and/or a hydrogenated or partially hydrogenated C5/C9 resin,and wherein: the Oligomer having a molecular weight of less than 300g/mol is less than 0.15, or the Oligomer having a molecular weight ofless than 600 g/mol is less than 0.45; (g) the modified thermoplasticresin is hydrogenated or partially hydrogenated C9 resin, the value ofTg/Mz is greater than 0.19 K/(g/mol), and wherein: the Oligomer having amolecular weight of less than 300 g/mol is less than or equal to 0.08 or0.05 or 0.02, and the Oligomer having a molecular weight of less than600 g/mol is less than 0.3; and/or (h) the modified thermoplastic resinis a hydrogenated or partially hydrogenated PMR resin, and: the value ofTg/Mz is greater than or equal to 0.30 K/(g/mol), the Oligomer having amolecular weight of less than 300 g/mol is less than 0.08, or theOligomer having a molecular weight of less than 600 g/mol is less than0.40, or the value of Tg/Mz is less than 0.30 K/(g/mol), the Oligomerhaving a molecular weight of less than 300 g/mol is less than 0.09, orthe Oligomer having a molecular weight of less than 600 g/mol is lessthan 0.25.

In one such embodiment, the modified thermoplastic resin is a PMR resinand/or a modified hydrogenated or partially hydrogenated PMR resin, andwhen Oligomer has a molecular weight of less than 300 g/mol, S isgreater than 2000. In another such embodiments, the modifiedthermoplastic resin is a hydrogenated or partially hydrogenated C9resin, and where Oligomer has a molecular weight of less than 300 g/mol,S is greater than 90. In other similar embodiments, where the modifiedthermoplastic resin is defined by Formula I, the modified thermoplasticresin has a glass transition temperature (Tg) of between −50° C. and160° C., between 0° C. and 140° C., or between 20° C. and 120° C.,and/or the number average molecular weight (Mn) of the modifiedthermoplastic resin is less than or equal to 1,000 g/mol, 500 g/mol, or250 g/mol, and/or wherein the z-average molecular weight (Mz) is lessthan or equal to 9,000 g/mol, 8,000 g/mol, or 6,000 g/mol.

Further embodiments of such modified thermoplastic resins defined byFormula I possess one or more of the following properties when theoligomer content is determined by GPC: (a) the modified thermoplasticresin is a PMR resin, and (i) for Oligomer having a molecular weight ofless than 600 g/mol, S is greater than 14, or (ii) for Oligomer having amolecular weight of less than 300 g/mol, S is greater than 67; (b) themodified thermoplastic resin is a C5 resin, and (i) for Oligomer havinga molecular weight of less than 600 g/mol, S is greater than 8, or (ii)for Oligomer having a molecular weight of less than 300 g/mol, S isgreater than 36; (c) the modified thermoplastic resin is a C5/C9 resin,and (i) for Oligomer having a molecular weight of less than 600 g/mol, Sis greater than 8, or (ii) for Oligomer having a molecular weight ofless than 300 g/mol, S is greater than 36; (d) the modifiedthermoplastic resin is a C9 resin, the value of Tg/Mz is greater than0.09 K/(g/mol), and (i) for Oligomer having a molecular weight of lessthan 600 g/mol, S is greater than 8, or (ii) for Oligomer having amolecular weight of less than 300 g/mol, S is greater than 38; (e) themodified thermoplastic resin is a hydrogenated or partially hydrogenatedDCPD resin, and (i) for Oligomer having a molecular weight of less than600 g/mol, S is greater than 5, or (ii) for Oligomer having a molecularweight of less than 300 g/mol, S is greater than 17; (f) the modifiedthermoplastic resin is a hydrogenated or partially hydrogenated C5 resinand/or a hydrogenated or partially hydrogenated C5/C9 resin, and (i) forOligomer having a molecular weight of less than 600 g/mol, S is greaterthan 5, or (ii) for Oligomer having a molecular weight of less than 300g/mol, S is greater than 10; (g) the modified thermoplastic resin ishydrogenated or partially hydrogenated C9 resin, the value of Tg/Mz isgreater than or equal to 0.19 K/(g/mol), and (i) for Oligomer having amolecular weight of less than 600 g/mol, S is greater than 6, or (ii)for Oligomer having a molecular weight of less than 300 g/mol, S isgreater than 29; and/or (h) the modified thermoplastic resin is ahydrogenated or partially hydrogenated PMR resin, and: the value ofTg/Mz is greater than or equal to 0.30 K/(g/mol), and (i) for Oligomerhaving a molecular weight of less than 600 g/mol, S is greater than 8,or (ii) for Oligomer having a molecular weight of less than 300 g/mol, Sis greater than 26; or the value of Tg/Mz is less than 0.30 K/(g/mol),and (i) for Oligomer having a molecular weight of less than 600 g/mol, Sis greater than 2, or (ii) for Oligomer having a molecular weight ofless than 300 g/mol, S is greater than 5.

In such embodiments, where the modified thermoplastic resins are definedas in Formula I, the high resolution TGA analysis is conducted using athermal gravimetric analyzer calibrated by curie point of magnetictransition standards according to ASTM method E1582, procedure C; and/orwherein the high resolution TGA analysis is conducted using a TAInstruments Q500 thermal gravimetric analyzer with sensitivity set to2.0 and resolution set to 3.0 by heating the modified thermoplasticresin in nitrogen with a scanning rate of 20 degrees per minute fromambient temperature to 625° C., and/or the GPC analysis is conducted at30° C. in tetrahydrofuran solvent at a flow rate of 1 ml/min with a GPCinstrument comprising a refractive index detector, a highly cross-linkedpolystyrene-divinylbenzene gel column, and/or a column comprisingpolymer particles with a nominal particle size of 6 μm.

BRIEF DESCRIPTION OF THE DRAWINGS

The invention will now be described with reference to the drawings. Theaccompanying drawings, which are incorporated in and constitute a partof this specification, illustrate certain embodiments, and together withthe written description, serve to explain certain principles of theconstructs and methods disclosed herein.

FIG. 1A, FIG. 1B, FIG. 1C, and FIG. 1D are correlation plots showing thelinear relationship between percent oligomer as determined by highresolution thermal gravimetric analysis (TGA) versus gel permeationchromatography (GPC) using polystyrene standards methods for bothmodified thermoplastic resins and unmodified thermoplastic resins. FIG.1A shows the GPC integrated percent area under the curve for moleculesless than 600 g/mol for standard resins (y=1.061x+12.13, R²=0.704) vs.percent oligomer determined by high resolution TGA. FIG. 1B shows theGPC integrated percent area under the curve for molecules less than 300g/mol for standard resins (y=0.9405x−13.73, R²=0.7206) vs. percentoligomer determined by high resolution TGA. FIG. 1C shows the GPCintegrated percent area under the curve for molecules less than 600g/mol for modified resins (y=1.5146x+19.422, R²=0.3404) vs. percentoligomer determined by high resolution TGA. FIG. 1D shows the GPCintegrated percent area under the curve for molecules less than 300g/mol for modified resins (y=0.4451x−0.9992, R²=0.5338) vs. percentoligomer determined by high resolution TGA.

FIG. 2 shows a plot of glass transition temperature (K) vs. molecularweight (g/mol) according to the Flory-Fox equation, revealing thecompositional property differences between thermoplastic resinspossessing an Mn value of less than about 5,000 g/mol and polymerspossessing an Mn value of greater than about 5,000 g/mol, based on gelpermeation chromatography (GPC) using polystyrene standards.

FIG. 3 shows the result of the separation of modified thermoplasticresin as measured with high resolution GPC.

FIG. 4A, FIG. 4B, and FIG. 4C show GPC traces of the startingthermoplastic resins Picco® AR85, Picco® A100, and Piccotac® 1095, andmodified thermoplastic resins of the same, respectively.

FIG. 5 shows an exemplary high resolution thermogravimetric analysis(TGA) trace showing weight loss versus temperature and the firstderivative of the trace for a modified DCPD thermoplastic resin.

FIG. 6 shows an exemplary trace showing weight loss versus temperatureand the first derivative of the trace for an unmodified PMRthermoplastic resin.

FIG. 7 shows an exemplary trace showing weight loss versus temperatureand the first derivative of the trace for a modified PMR thermoplasticresin.

FIG. 8 shows a spider diagram of the tire performance results ofKristalex® F-85, Kristalex® F-115, and the modified thermoplastic resin.

DETAILED DESCRIPTION

It is to be understood that the following detailed description isprovided to give the reader a fuller understanding of certainembodiments, features, and details of aspects of the invention, andshould not be interpreted as a limitation of the scope of the invention.

Definitions

Certain terms used throughout this disclosure are defined hereinbelow sothat the present invention may be more readily understood. Additionaldefinitions are set forth throughout the disclosure.

Each term that is not explicitly defined in the present application isto be understood to have a meaning that is commonly accepted by thoseskilled in the art. If the construction of a term would render itmeaningless or essentially meaningless in its context, the term'sdefinition should be taken from a standard dictionary.

The use of numerical values in the various ranges specified herein,unless expressly indicated otherwise, are considered to beapproximations as though the minimum and maximum values within thestated ranges were both preceded by the word “about.” In this context,the term “about” is meant to encompass the stated value±a deviation of1%, 2%, 3%, 4%, or not more than 5% of the stated value. In this manner,slight variations above and below the stated ranges can be used toachieve substantially the same results as the values within the ranges.In addition, the disclosure of these ranges is intended as a continuousrange including every value between the minimum and maximum values.

Unless otherwise indicated, % solids or weight % (wt %) are stated inreference to the total weight of a specific formulation, emulsion, orsolution.

Unless otherwise indicated, the terms “polymer” and “thermoplasticresin” do not necessarily mean the same thing, but include bothhomopolymers having the same recurring unit along the backbone, as wellas copolymers having two or more different recurring units along thebackbone. For instance, polymer refers to a molecule having a numberaveraged molecular weight of greater than 5,000 g/mol, as measured byGPC, whereas a “thermoplastic resin” refers to a molecule having anumber average molecular weight of less than 5,000 g/mol, as measured byGPC. Such polymers or thermoplastic resins include but are not limitedto, materials prepared by either condensation, cationic, anionic,Ziegler-Natta, reversible addition-fragmentation chain-transfer (RAFT),or free radical polymerization. Further, the term “thermoplastic resin”or “starting thermoplastic resin” when used alone refers to theunmodified, or non-modified thermoplastic resin. Furthermore, while theterm “polymer” is meant to encompass elastomers, the term “elastomer”does not necessarily encompass all polymers. In other words, as known toone of skill in the art, not all polymers are elastomers.

The term “comprising” (and its grammatical variations) as used herein isused in the inclusive sense of “having” or “including” and not in theexclusive sense of “consisting only of.”

The terms “a” and “the” as used herein are understood to encompass oneor more of the components, i.e., the plural as well as the singular.

The stated “phr” means parts per hundred parts of rubber by weight, andis used in this specification to mean the conventional stated amount inthe rubber industry for blend recipes. The dosage of the parts by weightof the individual substances in this context is always based on 100parts by weight of the total weight of all the rubbers present in theblend. The abovementioned thermoplastic resins are not considered to bea rubber in the context of this disclosure.

A “thermoplastic polymer” refers to a polymer having a number averagemolecular weight of greater than 5,000 g/mol, as measured by GPC, thathas no covalently crosslinked sites between individual polymermacromolecules and becomes liquid, pliable, or moldable above a specifictemperature, and then it returns to a solid state upon cooling. In manyinstances, the thermoplastic polymers are also soluble in appropriateorganic solvent media.

The term “vulcanized” as used herein means subjecting a chemicalcomposition, such as a polymer, for example an elastomeric and/orthermoplastic polymer composition, to a chemical process includingaddition of sulfur or other similar curatives, activators, and/oraccelerators at a high temperature. (See, for example, WO 2007/033720,WO 2008/083242, and PCT/EP2004/052743). The curatives and acceleratorsact to form cross-links, or chemical bridges, between individual polymerchains. Curing agents collectively refer to sulfur vulcanizing agentsand vulcanization accelerators. Suitable sulfur vulcanizing agentsinclude, for example, elemental sulfur (free sulfur) or sulfur donatingvulcanizing agents that make sulfur available for vulcanization at atemperature of about 140° C. to about 190° C. Suitable examples ofsulfur donating vulcanizing agents include amino disulfide, polymericpolysulfide, and sulfur olefin adducts. The polymer compositionsdescribed herein that are capable of being vulcanized can in someembodiments also include one or more vulcanizing accelerators.Vulcanizing accelerators control the time and/or temperature requiredfor vulcanization and affect the properties of the vulcanizate.Vulcanization accelerators include primary accelerators and secondaryaccelerators. Suitable accelerators include, for example, one or more ofmercapto benzothiazole, tetramethyl thiuram disulfide, benzothiazoledisulfide, diphenyl guanidine, zinc dithiocarbamate, alkylphenoldisulfide, zinc butyl xanthate,N-dicyclohexyl-2-benzothiazolesulfenamide, N-cyclohexyl-2-benzothiazolesulfenamide, N-oxydiethylene benzothiazole-2-sulfenamide, N,N-diphenylthiourea, dithiocarbamyl sulfenamide, N,N-diisopropylbenzothiazole-2-sulfenamide, zinc-2-mercapto toluimidazole, dithiobis(N-methyl piperazine), dithio bis(N-beta-hydroxy ethyl piperazine),and dithio bis(dibenzyl amine). Other vulcanizing accelerators include,for example, thiuram, and/or morpholine derivatives. Further, vulcanizedcompounds also in some embodiments include one or more silane couplingagents such as, for example, bifunctional organosilanes possessing atleast one alkoxy, cycloalkoxy, or phenoxy group on the silicon atom as aleaving group, and as the other functionality, having a group that canoptionally undergo a chemical reaction with the double bonds of thepolymer after splitting. The latter group may, for example, constitutethe following chemical groups: SCN, —SH, —NH2 or -Sx- (where x is from 2to 8). Thus, vulcanizates, i.e. mixtures to be vulcanized include insome embodiments various combinations of exemplary silane couplingagents such as 3-mercaptopropyltriethoxysilane,3-thiocyanato-propyl-trimethoxysilane, or3,3′-bis(triethoxysilylpropyl)-polysulfide with 2 to 8 sulfur atoms suchas, for example, 3,3′-bis(triethoxysilylpropyl)tetrasulfide (TESPT), thecorresponding disulfide (TESPD), or mixtures of the sulfides with 1 to 8sulfur atoms having a differing content of the various sulfides, asdescribed in further detail below.

The term “M_(w)” as used herein is the weight-average molecular weightand is determined using gel permeation chromatography (GPC) according tomethodology described below. Values reported herein are reported aspolystyrene equivalent weights.

The term “Mn” when used herein means the number average molecular weightin g/mol, i.e. the statistical average molecular weight of all polymerchains in the sample, or the total weight of all the molecules in apolymer sample divided by the total number of molecules present.

The term “Mz” when used herein means the z-average molecular weight ing/mol and is determined typically by sedimentation equilibrium(ultracentrifugation) and light scattering. Here Mz is determined by gelpermeation chromatography (GPC) according to methods described below. Mzis the thermodynamic equilibrium position of a polymer where the polymermolecule becomes distributed according to its molecular size. This valueis used in some instances as an indication of the high molecular weighttail in the thermoplastic resin.

The term “T₁₀” as used herein means the temperature (in degrees Celsius)at which the modified thermoplastic resin loses about 10% of itsstarting weight as measured by high resolution thermal gravimetricanalysis (TGA) using the methodologies described below.

“High resolution thermogravimetric analysis” (high resolution TGA) asused herein indicates an extension to conventional TGA wherein theheating rate is varied as a function of sample weight loss rate, e.g.sample decomposition rate changes. Faster decomposition rates triggerlower heating rates in Hi-Res TGA. The high resolution (Hi-Res) TGAapproach allows the use of high heating rates during no weight lossregions, then automatically reduces the heating rate during a weightloss transition. Thus, Hi-Res TGA enhances the resolution of multiplecomponents in a mixed polymer system, such as resin compositions. (See,for instance, Salin et al., “Kinetic analysis of high-resolution TGAvariable heating rate data,” J. Appl. Polym. Sci., 47: 847-856 (1993),and Sepe, M. P., “Thermal Analysis of Polymers,” Volume 95 of RAPRATechnology Limited Shawbury: Rapra review reports, iSmithers RapraPublishing, 1997). Note that whenever “TGA” is recited herein, theindicated technique is “high resolution” TGA in all instances.

“Glass transition temperature (Tg)” is a second order transition and isthe temperature range at which amorphous material reversibly changesfrom a hard, rigid, or “glassy” solid state to a more pliable,compliant, or “rubbery” viscous state, and is measured in degreesCelsius or degrees Fahrenheit. Tg is not the same as meltingtemperature. Tg can be determined using Differential Scanningcalorimetry (DSC) as disclosed below at Example 2.

“Modified thermoplastic resin” when used herein means a thermoplasticresin that has been processed or treated to remove a percentage ofdimers, trimers, tetramers, and/or pentamers (oligomers) of theunmodified thermoplastic resin. Thermoplastic resin means any knownthermoplastic resin that has a number average molecular weight of lessthan 5,000 g/mol as measured by GPC using, for instance, the GPCmethodologies described below.

“Unmodified thermoplastic resin” when used herein means a thermoplasticresin, or starting thermoplastic resins, such as PMR, C5, C5/C9, C9,DCPD, terpene/polyterpene, and indene-coumarone (IC), as describedhereinbelow. Thermoplastic resin means any known thermoplastic resinthat has a number average molecular weight of less than 5,000 g/mol asmeasured by GPC. Unmodified thermoplastic resins include hydrogenated,partially-hydrogenated, and non-hydrogenated versions of these resins.For instance, DCPD includes aromatic-modified DCPD, as well ashydrogenated and partially hydrogenated DCPD and/or hydrogenated andpartially hydrogenated aromatic-modified DCPD. C9 resin includes, forexample hydrogenated and partially hydrogenated aliphatic-modified C9,hydrogenated C9, and hydrogenated and partially hydrogenatedaliphatic-modified C9 resins. Likewise, PMR resins includes hydrogenatedand partially hydrogenated PMR and C5 includes hydrogenated andpartially hydrogenated C5 resin.

The term “PMR” as used herein means pure monomer thermoplastic resins.Pure monomer thermoplastic resins are produced from the polymerizationof styrene-based monomers, such as, styrene, alpha-methyl styrene, vinyltoluene, and other alkyl substituted styrenes. Pure monomerthermoplastic resins are produced by any method known in the art. Puremonomer feedstock for the production of pure monomer thermoplasticresins are in some cases synthetically generated or highly purifiedmonomer species. For example, styrene can be generated from ethylbenzene or alpha methyl styrene from cumene. In one embodiment, puremonomer hydrocarbon thermoplastic resins are prepared by cationicpolymerization of styrene-based monomers such as styrene, alpha-methylstyrene, vinyl toluene, and other alkyl substituted styrenes usingFriedel-Crafts polymerization catalysts such as Lewis acids (e.g., borontrifluoride (BF₃), complexes of boron trifluoride, aluminum trichloride(AlCl₃), and alkyl aluminum chlorides). Solid acid catalysts can also beutilized to produce pure monomer thermoplastic resins. The pure monomerthermoplastic resins disclosed herein are non-hydrogenated, partiallyhydrogenated, or fully hydrogenated resins. The term “hydrogenated” asused herein is also indicated alternatively in the shorthand “H2” andwhen H2 is used preceding or following a resin type it is intended toindicate that resin type is hydrogenated or partially hydrogenated, suchas “PMR H2” and “C5 H2” for example. When “H2” is used herein, “H2” ismeant to encompass both fully hydrogenated resin samples and partiallyhydrogenated resin samples. Thus, “H2” refers to the condition in whichthe resin is either fully hydrogenated or at least partiallyhydrogenated. Pure monomer thermoplastic resins are in some instancesobtained as Piccolastic® styrenic hydrocarbon thermoplastic resins,Kristalex® styrenic/alkyl styrenic hydrocarbon thermoplastic resins,Piccotex® alkyl styrenic hydrocarbon thermoplastic resins, and Regalrez®hydrogenated or partially hydrogenated pure monomer thermoplastic resinsfrom Eastman Chemical Company (Kingsport, Tenn., US).

The term “C5 thermoplastic resin” as used herein means aliphatic C5hydrocarbon thermoplastic resins that are produced from thepolymerization of monomers comprising C5 and/or C6 olefin speciesboiling in the range from about 20° C. to about 200° C. at atmosphericpressure. These monomers are typically generated from petroleumprocessing, e.g. cracking. The aliphatic C5 hydrocarbon thermoplasticresins of this invention can be produced by any method known in the art.In one embodiment, aliphatic C5 hydrocarbon thermoplastic resins areprepared by cationic polymerization of a cracked petroleum feedcontaining C5 and C6 paraffins, olefins, and diolefins also referred toas “C5 monomers.” These monomer streams are comprised of cationicallypolymerizable monomers such as 1,3-pentadiene which is the primaryreactive component along with cyclopentene, pentene, 2-methyl-2-butene,2-methyl-2-pentene, cyclopentadiene, and dicyclopentadiene. Thepolymerizations are catalyzed using Friedel-Crafts polymerizationcatalysts such as Lewis acids (e.g., boron trifluoride (BF₃), complexesof boron trifluoride, aluminum trichloride (AlCl₃), and alkyl aluminumchlorides). In addition to the reactive components, nonpolymerizablecomponents in the feed include saturated hydrocarbons that are in someinstances co-distilled with the unsaturated components such as pentane,cyclopentane, or 2-methylpentane. Solid acid catalysts can also beutilized to produce aliphatic C5 hydrocarbon thermoplastic resins.Aliphatic C5 hydrocarbon thermoplastic resins include non-hydrogenated,partially hydrogenated, or fully hydrogenated resins. Aliphatic C5thermoplastic resins can be obtained as Piccotac® C5 and Eastotac® C5 H2thermoplastic resins from Eastman Chemical Company (Kingsport, Tenn.,US).

The term “C5/C9 thermoplastic resin” as used herein means analiphatic/aromatic hydrocarbon C5/C9 thermoplastic resin that isproduced from the polymerization of monomers comprising at least oneunsaturated aromatic C8, C9, and/or C10 species boiling in the rangefrom about 100° C. to about 300° C. at atmospheric pressure and at leastone monomer comprising C5 and/or C6 olefin species boiling in the rangefrom about 20° C. to about 200° C. at atmospheric pressure. In oneembodiment, C5 and/or C6 species include paraffins, olefins, anddiolefins also referred to as “C5 monomers.” These monomer streams arecomprised of cationically polymerizable monomers such as 1,3-pentadienewhich is the primary reactive component along with cyclopentene,pentene, 2-methyl-2-butene, 2-methyl-2-pentene, cyclopentadiene, anddicyclopentadiene. In one embodiment, unsaturated aromatic C8, C9,and/or C10 monomers are derived from petroleum distillates resultingfrom naphtha cracking and are referred to as “C9 monomers.” Thesemonomer streams are comprised of cationically polymerizable monomerssuch as styrene, alpha methyl styrene, beta-methyl styrene, vinyltoluene, indene, dicyclopentadiene, divinylbenzene, and other alkylsubstituted derivatives of these components. The cationic polymerizationis in some instances catalyzed using Friedel-Crafts polymerizationcatalysts such as Lewis acids (e.g., boron trifluoride (BF₃), complexesof boron trifluoride, aluminum trichloride (AlCl₃), and alkyl aluminumchlorides). Solid acid catalysts are also utilized to producealiphatic/aromatic C5/C9 hydrocarbon thermoplastic resins. In additionto the reactive components, non-polymerizable components include,aromatic hydrocarbons such as xylene, ethyl benzene, cumene, ethyltoluene, indane, methylindane, naphthalene and other similar specifies.The non-polymerizable components of the feed stream are in someembodiments incorporated into the thermoplastic resins via alkylationreactions. Aliphatic/aromatic C5/C9 hydrocarbon thermoplastic resinsinclude non-hydrogenated, partially hydrogenated resins, andhydrogenated resins. Aliphatic/aromatic C5/C9 thermoplastic resins canbe obtained as Piccotac® thermoplastic resin from Eastman ChemicalCompany. The proportion of C5 to C9 is not limited. In other words, theamount of C5 monomer in the C5/C9 thermoplastic resin can be anywherefrom 0.1 to 100% and vice versa the amount of C9 monomer in the C5/C9thermoplastic resin can be from 0.1 to 100%.

The term “C9 thermoplastic resin” as used herein means an aromatic C9hydrocarbon thermoplastic resin that is a thermoplastic resin producedfrom the polymerization of monomers comprising unsaturated aromatic C8,C9, and/or C10 species boiling in the range from about 100° C. to about300° C. at atmospheric pressure. These monomers are typically generatedfrom petroleum processing, e.g. cracking. The aromatic C9 hydrocarbonthermoplastic resins of this invention can be produced by any methodknown in the art. Aromatic C9 hydrocarbon thermoplastic resins are inone embodiment prepared by cationic polymerization of aromatic C8, C9,and/or C10 unsaturated monomers derived from petroleum distillatesresulting from naphtha cracking and are referred to as “C9 monomers.”These monomer streams are comprised of cationically polymerizablemonomers such as styrene, alpha methyl styrene (AMS), beta-methylstyrene, vinyl toluene, indene, dicyclopentadiene, divinylbenzene, andother alkyl substituted derivatives of these components. Aliphaticolefin monomers with four to six carbon atoms are also present duringpolymerization in some embodiments of C9 resins. The polymerization isin some instances catalyzed using Friedel-Crafts polymerizationcatalysts such as Lewis acids (e.g., boron trifluoride (BF₃), complexesof boron trifluoride, aluminum trichloride (AlCl₃), and alkyl aluminumchlorides). In addition to the reactive components, nonpolymerizablecomponents include, but are not limited to, aromatic hydrocarbons suchas xylene, ethyl benzene, cumene, ethyl toluene, indane, methylindane,naphthalene, and other similar chemical species. The nonpolymerizablecomponents of the feed stream are in some embodiments incorporated intothe thermoplastic resins via alkylation reactions. C9 hydrocarbonthermoplastic resins include non-hydrogenated, partially hydrogenated,or fully hydrogenated resins. Aromatic C9 hydrocarbon thermoplasticresins can be obtained as Picco® C9 thermoplastic resin, and aliphatichydrogenated and aliphatic/aromatic partially hydrogenated C9 H2hydrocarbon thermoplastic resins can be obtained as Regalite®thermoplastic resin from Eastman Chemical Company.

The term “DCPD thermoplastic resin” as used herein meansdicyclopentadiene (DCPD) thermoplastic resin, most commonly formedthrough ring opening metathesis polymerization (ROMP) ofdicyclopentadiene in the presence of a strong acid catalyst, such asmaleic acid or aqueous sulphuric acid, or thermal polymerization.Dicyclopentadiene is also formed in some embodiments by a Diels Alderreaction from two cyclopentadiene molecules and exists in twostereo-isomers: endo-DCPD and exo-DCPD. Typically, greater than 90% ofthe DCPD molecules present in commercial grades of DCPD are in the endoform. DCPD thermoplastic resins include aromatic-modified DCPD resins aswell as hydrogenated, partially hydrogenated, and non-hydrogenatedresins, though in most instances herein only H2 DCPD is described sinceit is the most readily commercially available form of DCPD.Aromatic-modified DCPD is also contemplated as a DCPD thermoplasticresin. Aromatic modification is, for instance, by way of C9 resin oil,styrene, or alpha methyl styrene (AMS), and the like. Hydrogenated andpartially hydrogenated DCPD and hydrogenated and partially hydrogenatedaromatic-modified DCPD resin is commercially available as Escorez®5000-series resin (ExxonMobil Chemical Company, TX, US).

The term “terpene thermoplastic resin” or “polyterpene resin” as usedherein means thermoplastic resins produced from at least one terpenemonomer. For example, α-pinene, β-pinene, d-limonene, and dipentene canbe polymerized in the presence of aluminum chloride to providepolyterpene thermoplastic resins. Other examples of polyterpenethermoplastic resins include Sylvares® TR 1100 and Sylvatraxx® 4125terpene thermoplastic resin (AZ Chem Holdings, LP, Jacksonville, Fla.,US), and Piccolyte® A125 terpene thermoplastic resin (Pinova, Inc.,Brunswick, Ga., US). Terpene thermoplastic resins can also be modifiedwith aromatic compounds. Sylvares® ZT 105LT and Sylvares® ZT 115 LTterpene thermoplastic resins are aromatically modified (Az ChemHoldings, LP, Jacksonville, Fla., US).

The term “IC thermoplastic resin” or “IC resin” as used herein meansindene-coumarone (IC) thermoplastic resin, i.e. a syntheticthermoplastic terpene resin formed using feedstocks of indene andcoumarone made from heavy-solvent naphtha obtained from the distillationof coal tar, which is a by-product of coke production. Heavy-solventnaphtha is rich in coumarone and indene, but most especially indene, andcan be modified with phenol. These feedstocks can be formed bypolymerization in BF₃ or BF₃ etherates. Catalysts can be removed by analkaline wash or lime after polymerization. The resin can be isolated bysteam distilling off the unreacted naphtha. IC thermoplastic resins canbe used as plasticizers, and secure stress-strain properties at highlevels. Examples of such resins include Novares® C indene-coumarone andNovares® CA phenol-modified indene-coumarone thermoplastic resin, whichare commercially available from Rutgers Germany GmbH, Duisburg, Germany.

It is to be understood that encompassed by the above definitions ofcertain types of thermoplastic resins, such as DCPD, PMR, C5, C9, C5/C9,IC, terpene, and the like, including hydrogenated,partially-hydrogenated, and non-hydrogenated versions of these resins,that these thermoplastic resins include resins of similar typesgenerated by mixing or blending of dissimilar feedstocks to produceheterogeneous mixtures of the feedstocks used to generate thethermoplastic resins. Furthermore, it is to be understood that at leastwith respect to the PMR and terpene thermoplastic resins discussedherein these thermoplastic resins encompass various known derivatives ofsuch thermoplastic resins such as phenol-modified and rosin-modifiedversions of the resins.

The term “thermoplastic resin oligomers” or “oligomer” refers to thedimer, trimer, tetramer, and/or pentamer species of polymerized monomersthat comprise the thermoplastic resin.

The term “dimer” as used herein means a moiety encompassing twocovalently linked units of a monomer. For instance, in the synthesis ofa thermoplastic resin by way of polymerization of one or more types ofmonomers, a dimer is a species comprising two of the monomers. The dimermay either be a homodimer or heterodimer or a mixture of combinationsthereof.

The term “trimer” as used herein means a moiety encompassing threecovalently linked units of a monomer. For instance, in the synthesis ofa thermoplastic resin by way of polymerization of one or more types ofmonomers, a trimer is a species comprising three of the monomers. Thetrimer may either be a homotrimer or heterotrimer or a mixture ofcombinations thereof.

The term “tetramer” as used herein means a moiety encompassing fourcovalently linked units of a monomer. For instance, in the synthesis ofa thermoplastic resin by way of polymerization of one or more types ofmonomers, a tetramer is a species comprising four of the monomers. Thetetramer may either be a homotetramer or heterotetramer or a mixture ofcombinations thereof.

The term “pentamer” as used herein means a moiety encompassing fivecovalently linked units of a monomer. For instance, in the synthesis ofa thermoplastic resin by way of polymerization of one or more types ofmonomers, a pentamer is a species comprising five of the monomers. Thepentamer may either be a homopentamer or heteropentamer or a mixture ofcombinations thereof. The term “oligomer” or “oligomers” as used hereinmeans a mixture or combination of dimers, trimers, tetramers, andpentamers.

Modified Resins

Disclosed herein are modified hydrocarbon thermoplastic resins that arelow molecular weight polymeric structures, i.e. Mn less than about 5,000g/mol, polymerized from a mixture of different monomers or a singlemonomer. Thermoplastics and thermoplastic resins are polymers that turnto liquid when heated and turn solid when cooled. They can be repeatedlyre-melted and remolded, allowing parts and scraps to be reprocessed. Inmost cases, such thermoplastic resins are also very recyclable.Amorphous thermoplastic resins have a randomly ordered molecularstructure that does not possess a sharp melt point. Instead, amorphousmaterials soften gradually as the temperature rises. These materialschange viscosity when heated. Amorphous thermoplastic resins areisotropic in flow, shrinking uniformly in the direction of flow andtransverse to flow. As a result, amorphous materials typically exhibitlower mold shrinkage and less tendency to warp than the semi-crystallinethermoplastic materials. Amorphous thermoplastic resins tend to losetheir strength quickly at temperatures above their glass transitiontemperature (Tg). Above its glass transition temperature, Tg, and belowits melting point, Tm, if semi-crystalline, the physical properties of athermoplastic change drastically without an associated phase change.Within this temperature range, most thermoplastics are rubbery due toalternating rigid crystalline regions, if present, and elastic amorphousregions, approximating random coils.

The polymerization of thermoplastic resins from monomer units istypically performed in organic solvent according to known procedures inthe art. The solvent is then removed by evaporation after thepolymerization process resulting in the hydrocarbon thermoplastic resin.During the evaporation process the solvent is selectively removed, butmost oligomers (dimer, trimer, tetramer, and/or pentamer species) remainin the polymerized hydrocarbon thermoplastic resin.

However, improvement of such thermoplastic resins is sometimes desiredto obtain more desirable physical properties in various applications(noted below). It has been surprisingly discovered that by selectivelyremoving a percentage of the low molecular weight oligomers ofpolymerized thermoplastic resins, the Tg of the modified thermoplasticresin created thereby is increased with respect to non-modifiedthermoplastic resins. Decreasing the relative amount of the lowmolecular weight dimer, trimer, tetramer, and pentamer species inmodified thermoplastic resins as compared to unmodified thermoplasticresins is accomplished without increasing the amount of high molecularweight species in the modified thermoplastic resin. When used in someapplications, for instance in an elastomeric tire tread compound, suchmodified thermoplastic resins provide surprisingly improved wet gripversus rolling resistance performance balance.

Thermoplastic resins useful in this regard, i.e. thermoplastic resinsthat benefit from modification as disclosed herein, include, but are notlimited to, the following: PMR, DCPD, C5, C9, C5/C9, terpene, and ICthermoplastic resins, for example, as well as hydrogenated,partially-hydrogenated, and non-hydrogenated versions of these resins.Other resins known in the art can also be amendable to the disclosedmodification process to produce similar marked improvements in resincompositions incorporating the disclosed modified thermoplastic resins.

Thus, especially in elastomeric rubber compositions comprisingthermoplastic resins, it is desired that the following thermoplasticresin parameters be optimized: low oligomer content, resulting in a highvalue of Tg to obtain the largest impact on the viscoelastic propertiesof thermoplastic resin-elastomer blends, and a low Mz value to maintainfull thermoplastic resin-elastomer compatibility.

The modified thermoplastic resins disclosed herein are thereforemodified in the sense that the amount of relatively low molecular weightspecies, i.e. thermoplastic resin species (monomers, dimers, trimers,tetramers, and/or pentamers) having a molecular weight (Mn) value ofless than about 600 g/mol, or 300 g/mol, are decreased as compared withthe corresponding unmodified thermoplastic resins. The feedstock for themodified thermoplastic resins is typically derived from petroleum, pinetree, citrus peel, or hydrocarbon monomers. The glass transitiontemperature (Tg) of the disclosed modified thermoplastic resins dependson the number average molecular weight (Mn). This characteristic isdescribed by the Flory-Fox equation (Formula II):T _(g)(M _(n))≈T _(g,∞) −K/M _(n)  II

The Tg and Mn values of the Flory-Fox equation are as defined herein.The symbol T_(g, ∞) is defined as the maximum glass transitiontemperature that can be achieved at a theoretical infinite molecularweight. The value of K is the empirical constant related to the freevolume present in the polymer thermoplastic resin sample. Thisrelationship shows that polymeric thermoplastic resins with an Mn valueof greater than 5,000 g/mol (polymers) possess a constant Tg, whilepolymeric structures with an Mn value of less than 5,000 g/mol(thermoplastic resins) show a strong dependence of the value of Tg onthe value of Mn. Given this definition, it is clear to one of skill thatthermoplastic resins differ in composition from polymers.

Thus, disclosed are modified thermoplastic resins that achieve a high Tgvalue while maintaining to a large degree the original Mn value of thecorresponding non-modified thermoplastic resin. In one embodiment, theTg value of the modified thermoplastic resin is from about −50° C. to160° C. In another embodiment, the Tg value is from about 0° C. to 140°C. In a further embodiment, the Tg value of the modified thermoplasticresin is from about 20° C. to 120° C. The Tg value of the modifiedthermoplastic resin may be anywhere from −50° C., −40° C., −30° C., −20°C., −10° C., 0° C., 10° C., 20° C., or 30° C., to anywhere from 120° C.,130° C., 140° C., 150° C., and 160° C. and all ranges includedtherebetween.

In one embodiment, the modified thermoplastic resins disclosed hereinpossess a number average molecular weight (Mn) having a value of lessthan about 1,000 g/mol. In another embodiment, the Mn value of themodified thermoplastic resin is less than about 850 g/mol. In yetanother embodiment, the Mn value of the modified thermoplastic resin isless than about 900 g/mol. However, the Mn value of the modifiedthermoplastic resin can be any value of less than about 1,000 g/mol, 950g/mol, 900 g/mol, 850 g/mol, 800 g/mol, 750 g/mol, 700 g/mol, 650 g/mol,600 g/mol, 550 g/mol, 500 g/mol, 450 g/mol, 400 g/mol, 350 g/mol, 300g/mol, and 250 g/mol.

The amount of oligomer species present in the modified thermoplasticresin, in other words the fraction of the modified thermoplastic resinthat is composed of dimers, trimers, tetramers, and/or pentamer, asdetermined by high resolution TGA, is in one embodiment less than about38 wt %. In another embodiment, the amount of oligomeric species presentin the modified thermoplastic resin is less than about 15 wt %. In yetanother embodiment, the amount of oligomer species present in themodified thermoplastic resin is less than about 10 wt %. It should benoted that since different thermoplastic resins comprise differentamounts of monomers, dimers, trimers, tetramers, and/or pentamers, theamount of each specific species may change, or may remain the same.However, overall, the amount of the sum of all of these species is lessthan about 40 wt %, 10 wt %, or even less than about 5 wt %. In otherembodiments, the amount of oligomeric species present in the modifiedthermoplastic resin is less than about 40 wt %, 38 wt %, 36 wt %, 34 wt%, 32 wt %, 30 wt %, 28 wt %, 26 wt %, 24 wt %, 22 wt %, 20 wt %, 18 wt%, 16 wt %, 14 wt %, 12 wt %, 10 wt %, 9 wt %, 8 wt %, 7 wt %, 6 wt %, 5wt %, or even about 4 wt % of the total thermoplastic resin in themodified thermoplastic resin.

The z-average molecular weight, Mz, of the modified thermoplastic resinsis preferably less than about 9,500 g/mol, more preferably less thanabout 8,000 g/mol, and most preferably less than about 6,000 g/mol. Inother embodiments, the modified thermoplastic resin possesses an Mzvalue of less than about 9,000 g/mol, 8,500 g/mol, 8,000 g/mol, 7,500g/mol, 7,000 g/mol, 6,500 g/mol, 6,000 g/mol, 5500 g/mol, 5000 g/mol,4500 g/mol, 4000 g/mol, 3500 g/mol, 3000 g/mol, 2500 g/mol, 2000 g/mol,1500 g/mol, 1000 g/mol, or about 900 g/mol.

Values for Tg/Mz across all resin types, either modified or unmodified,are generally between about 0.02 K/(g/mol) to about 0.7 K/(g/mol).Standard resins generally possess an Mn value of as low as about 300g/mol, but lower values are possible.

The modified thermoplastic resins disclosed herein can be describedbased on other physical properties as well. In addition to the values ofMn, Tg, and percent of oligomeric species, the modified thermoplasticresins can be described by the relationship between the variables of thefollowing Formula I:

$\begin{matrix}{S = {\left( \frac{T_{g}}{M_{z}} \right){\text{/}\left\lbrack {{Oligomer} \times \left( {1 - \frac{T_{10}}{T_{\max}}} \right)} \right\rbrack}}} & I\end{matrix}$

-   -   wherein Tg is the glass transition temperature in degrees        Celsius of the thermoplastic resin;    -   wherein Mz is the z-average molecular weight of the        thermoplastic resin;    -   wherein “Oligomer” is the fractional percentage of oligomer        present in the modified thermoplastic resin as measured by high        resolution thermogravimetric analysis (TGA) or by gel permeation        chromatography (GPC), Oligomer being defined as dimer, trimer,        tetramer, and/or pentamer compounds of the monomer comprising        the thermoplastic resin polymer;    -   wherein T₁₀ is the temperature (in degrees Celsius) at which the        modified thermoplastic resin loses about 10% of its starting        weight as measured by high resolution thermal gravimetric        analysis (TGA); and    -   wherein T_(max) is the temperature (in degrees Celsius) of the        maximum first derivative value of the modified thermoplastic        resin as measured by high resolution thermal gravimetric        analysis (TGA).

The value of “S” according to the equation of Formula I of the modifiedthermoplastic resins depends directly on the manner in which the valueof Oligomer is measured, i.e., by high resolution TGA or GPC.Furthermore, the value of “S” depends also on whether, when Oligomer ismeasured by GPC, the value is referring to the fraction of resin havinga molecular weight below 600 g/mol or below 300 g/mol. These variousranges for the value of “S” are provided in Tables 1A and 1B, for GPCmeasurements, and Table 1C for high resolution TGA measurement.Additionally, as noted in Tables 1A, 1B, and 1C, the value of “S”depends on the resin type that is subjected to the modification process.For instance, as provided in Table 1B, the value of S as measured by GPCfor resins of the C5, C5/C9, C5 H2 and C5/C9 H2, C9, PMR, PMR H2, C9 H2,and DCPD H2 types, S values range from 2 to 30,000. However,theoretically, if Oligomer is as low as about 0.001, the value of S canbe as high as about 4,000,000 or more. For instance, in one embodiment,the value of Oligomer is about 0.01, and the value of S therefore is asmuch as 400,000 or more. Referring to Formula I again, the smallestmeasured delta for T₁₀/T_(max) is about 2.27 degrees apart. In such anembodiment where T₁₀/T_(max) is as low as about 2.27, and Oligomer is aslow as about 0.01, then the value of S is as high as about 784,000 orpossibly higher. Given the same parameters, in another embodiment, ifT₁₀/T_(max) is about 1, and Oligomer is as low as 0.01, then S in thisembodiment is as high as about 1,800,000.

The modified thermoplastic resins possess a value of T₁₀/T_(max) ofabout 0.70 to about 0.98. In other embodiments, the modifiedthermoplastic resins disclosed herein possess a T₁₀/T_(max) value ofgreater than or equal to about 0.75, 0.76, 0.77, 0.78, 0.79, 0.80, 0.85,0.90, 0.91, 0.92, 0.93, 0.94, 0.95 or even 0.98.

In certain embodiments, the modified thermoplastic resins having anMz<9,000 g/mol as disclosed herein possess a reduction in oligomercontent as compared with corresponding unmodified thermoplastic resins.The modified thermoplastic resin oligomer content is reflected in Table1A, 1B, and 1C, below, and as determined by GPC (Table 1A and Table 1B)or high resolution TGA (Table 1C) methodologies, said methodologiesdescribed in Example 2, below. Unmodified thermoplastic resin oligomervalues are provided for comparison in Table 2, below.

TABLE 1A Properties of Modified Thermoplastic Resins Having an Mz <9,000g/mol, as Determined by GPC (Polystyrene Equivalents) Tg/Mz (K/(g/mol))% Resin % Resin Resin Type Requirement AND/OR <300 g/mol AND/OR <600g/mol C5 — AND <3, <2, or <1 AND/OR <17, <10, or <5 C5/C9 — AND <3, <2,or <1 AND/OR <17, <10, or <5 C5 H2 and — AND <15, <10, or <5 AND/OR <45,<40, or <30 C5/C9 H2 C9 >0.09 AND <5, <3, or <1 AND <25, <20, or <15 PMR≥0.14 AND ≤2.5, <1, or <0.5 AND ≤19, <10, or <5 PMR H2 ≥0.30 AND <10,<5, or <3 AND/OR <45, <40, or <20 PMR H2 <0.30 AND <10, <5, or <3 AND/OR<30, <20, or <10 C9 H2 ≥0.19 AND ≤10, <7, or <5 AND <34, <30, or <25DCPD H2 >0.25 AND <16, <10, or <5 AND/OR <55,<45, or <40

TABLE 1B Properties of Modified Thermoplastic Resins Having an Mz <9,000g/mol, as Determined by GPC (Polystyrene Equivalents) S Value Tg/Mz SValue when S Value when (K/(g/mol)) Oligomer is <600 Oligomer is <300Resin Type Requirement AND/OR g /mol g/mol C5 — AND >8, >25, >100,or >36, >100, >1000, >200 or >2000 C5/C9 — AND 8, >25, >1000,or >36, >100, >1000, >2000 or >2000 C5 H2 and — AND >5, >20,or >50 >10, >20, or >50 C5/C9 H2 C9 >0.09 AND >8, >15, >50,or >100 >38, >50, >1000, or >3000 PMR —AND >14, >56, >100, >67, >100, >500, >500, or >1000 >1000, >5000,or >10,000 PMR H2 ≥0.30 AND >8, >12, >40, >26, >75, >125, >55,or >75 >300, >500, >1000, or >1500 PMR H2 <0.30AND >2, >15, >40, >5, >50, >100, >75, or >125 >500, >1000, or >2000 C9H2 ≥0.19 AND >6, >10, >35, or >45 >29, >60, >120, or >300 DCPD H2 —AND >5, >10, >50, or >80 >17, >40, >100, >500, or >1000

TABLE 1C Properties of Modified Thermoplastic Resins Having an Mz <9,000g/mol, as Determined by High Resolution TGA HIGH RESOLUTION TGA Tg/Mz(K/(g/mol)) T₁₀/T_(max) Resin class Requirement AND/OR S % Oligomer(×100) C5 — AND ≥5, >30, >50, <14, <8, or <4 ≥92, >94, >100, >300,or >98 >400, or >600 C5/C9 — AND ≥10, >30, <15, <8, or<4 >92, >94, >50, >100, >300, or >98 >400, or >600 C5 H2 and — AND≥10, >30, <30, <20, or <10 ≥90, >94, C5/C9 H2 >50, >100,or >98 >300, >400, or >600 C9 ≥0.12 AND ≥16, >30, >50, ≤15, <8, or <4≥88, >94, >100, >500, or >98 >1000, >2000, or >4000 PMR ≥0.14AND >12, >26, <17, <8, or <4 ≥90, >94, >50, >100, >500,or >98 >1000, >2000, or >4000 PMR H2 ≥0.30 AND ≥22, >30, >50, ≤16, <8,or <4 >85, >90, >100, >300, or >94 >600, >800, or >1000 PMR H2 <0.30 AND≥5, >30, >50, <38, <8, or <4 >75, >90, >100, >300,or >94 >600, >800, >1000,>1500, or >2000 C9 H2 ≥0.19 AND >16, >30, <13,<8, or <4 ≥90, >94, >50, >100, >150, or >98 >175, >200 or >220 DCPDH2 >0.25 AND ≥10, >30, >50, <31, <20, or <10 >85, >90, >100, >300,or >94 >600, >800, or >1000

That is, the fraction of the modified thermoplastic resins describedherein having a molecular weight of less than 600 g/mol as well as thefraction having a molecular weight of less than 300 g/mol, i.e., theoligomer percentage, is determined by gel permeation chromatography(GPC) in Table 1A and Table 1B. Table 1C also presents properties of themodified thermoplastic resins determined by high resolution TGA. GPC andhigh resolution TGA methodologies for determining the low molecularweight oligomer fractions (oligomers) of the modified resins are relatedin a linear manner. (See, FIGS. 1A, 1B, 1C, and 1D for correlations).

Thus, as set forth in Table 1A, for example, C5 and C5/C9 modifiedthermoplastic resins described herein possess no restrictions withregard to the Tg/Mz value, the percent modified resin having a molecularweight of less than 300 g/mol as determined by GPC is less than 3%, lessthan 2%, or less than 1%, and/or the percent modified resin having amolecular weight of less than 600 g/mol as determined by GPC is lessthan 17%, less than 10%, or less than 5%. That is, when determined byGPC analysis, the percent resin having a molecular weight of less than300 g/mol is a sufficient characteristic to define the modifiedthermoplastic resin of C5 and C5/C9. Likewise, the percent resin havinga molecular weight of less than 600 g/mol is a sufficient characteristicto define the modified thermoplastic resin of C5 and C5/C9. On the otherhand, Table 1A discloses that with respect to C9 resins, for example,both conditions must be met if being characterized by GPC. That is, theamount of oligomers having a molecular weight of less than 300 g/mol inmodified C9 resins is less than 5%, less than 3%, or less than 1%, andthe amount of oligomers having a molecular weight of less than 600 g/molin modified C9 resins is less than 25%, less than 20%, or less than 15%.Thus, for C9 resins, for example, both the stated conditions for %oligomer must be met to meet the definition of a modified thermoplasticresin. This is the meaning attributed to the “AND/OR” column in Table1A. Furthermore, Table 1A notes that these amounts of oligomers found inmodified thermoplastic C9 resins is true only when the modifiedthermoplastic C9 resins possess a Tg/Mz value greater than 0.09K/(g/mol).

Turning to Table 1B, it is observed that the S value, when measured byGPC, changes depending on whether the oligomer is defined as % resinbelow 600 g/mol or % resin below 300 g/mol. Referring to Formula I, itcan be readily understood that if the Oligomer term is in thedenominator of the fraction defining the value of S, then changing theOligomer cut off from less than 600 g/mol to less than 300 g/mol willimpact the value of S. Thus, Table 1B lists the different S values thatare possible when defining a modified thermoplastic resin, depending onwhether Oligomer is defined by a cut off of % resin below 600 g/mol ascompared with % resin below 300 g/mol. As with Table 1A, there areadditional qualifications in the definition of S in Table 1B withrespect to the value of Tg/Mz for certain starting resin types. Forinstance, when the starting resin type is C9 H2, then the values of Sprovided in Table 1B are only true for modified thermoplastic resinsthat also possess a Tg/Mz value of ≥0.19 (K/(g/mol)).

On the other hand, when analyzed by high resolution TGA, when the valueof Tg/Mz is as defined herein for a certain resin type as set forth inTable 1C, then the modified thermoplastic resins described hereinpossess any one or more of the characteristics provided in Table 1Cunder the “TGA” header. Thus, In Table 1C for example in the context ofstarting resin C5, S is greater than or equal to 5, and in someembodiments greater than 30, and in other embodiments greater than 50.Where there is a dash (“-”) indicated in any of Table 1A, 1B, or 1C,this means there is no further restriction on the Tg/Mz values withrespect to modified resin properties and that the indicated modifiedresin property values in the table for these resins applies across allTg/Mz values.

It is additionally noted that with respect to the “AND/OR”qualifications in Tables 1A, 1B, and 1C, if not otherwise stated, thequalification is “AND” or “OR.” In other words, if the “AND/OR” columnis not present, or if it is not otherwise stated, then either the firstcondition or the second condition (listed from left to right in theTable) must be met, or both the first condition and the second conditionmust be met to meet the definition of a modified thermoplastic resin asdescribed herein.

As can be seen in Tables 1A, 1B, and 1C, some modified resins of certainclasses, such as PMR, PMR H2, C9 H2, DCPD H2, and C9, in someembodiments, possess a specific Tg/Mz value, while other modifiedresins, such as C5, C5/C9, C5 H2, and C5/C9 H2, can be identifiedwithout reference to this value, since in the later embodiments themodified resins are sufficiently characterized or distinguished fromunmodified resins based solely on the percent resin oligomer of lessthan 300 g/mol and/or less than 600 g/mol (as determined by GPC).Likewise, when analyzing the modified resins by high resolution TGA,some modified resins of certain types such as PMR, PMR H2, C9 H2, DCPDH2, and C9, possess a specific Tg/Mz value, while other modified resinscan be identified without reference to this value, since in the laterembodiments the modified resins are sufficiently characterized ordistinguished from unmodified resins based solely on the percentoligomer as measured by high resolution TGA, S value, and/or T₁₀/T_(max)value.

In comparison to the values of Tables 1A, 1B, and 1C, correspondingunmodified thermoplastic resins of all resin types tested possess therelative amounts of oligomers as determined by GPC and high resolutionTGA as reflected in Table 2, below.

TABLE 2 Properties of Unmodified Thermoplastic Resins having an Mz <9,000 g/mol and Specified Tg/Mz Values GPC % Resin < % Resin < HIGHRESOLUTION TGA Resin Tg/Mz 300 600 Tg/Mz % T₁₀/T_(max) Type (K/(g/mol))g/mol g/mol (K/(g/mol)) S Oligomer (×100) C5 — 3-7 17-26 0.08-0.10 2-1013-31 71-89 C5/C9 — 3-7 17-26 0.04-0.11 3-6  17-21 81-84 C5 H2 — 16-2854-61 0.13-0.23 1-5  31-48 55-79 C9 <0.09  5-10 15-39 0.13-0.31 4-1616-42 66-87 PMR ≥0.14 3-9 15-31 0.14-0.30 2-11 17-52 72-91 PMR H2 —10-23 32-49 0.20-0.33 3-22 18-39 70-85 C9 H2 ≥0.19  8-28 23-70 0.19-0.533-11 21-57 65-81 DCPD >0.25  7-53 31-84 0.27-0.54 2-10 32-64 63-83 H2

Thus, it can be readily observed that the modified thermoplastic resinsdescribed herein possess substantially reduced amounts of oligomer ascompared to their unmodified counterparts, comparing Table 1 values toTable 2 values, at least as determined by GPC and high resolution TGAmethodologies.

To reduce the amount of the oligomeric fraction of the thermoplasticresins, that is, the dimer, trimer, tetramer, and/or pentamer species,several techniques known in the art are suitable, such as, but notlimited to, one or more of: membrane separation, selectiveprecipitation, selective polymerization conditions, evaporation anddistillation, and preparative gel permeation chromatography.

Membrane separation is commonly employed as a purification technique inthermoplastic resin chemistry. (See, for instance, Bowen et al., Chem.Eng. Res. Des., 76(8):885-893, 1998, and Llosa Tanco et al., Process,4(29):1-21, 2016). In this method, the membrane is typically a selectivebarrier that permits the separation of certain chemical species in aliquid by a combination of sieving and sorption diffusion mechanism.Membranes can selectively separate components of a liquid compositionbased on particle size, over a wide range of particle sizes andmolecular weights, from large polymeric, i.e. greater than 5,000 g/molMn, to low monomolecular materials. Given this ability, membraneseparation is a suitable technology to remove oligomeric speciesfractions from thermoplastic resins of many different types.

Selective precipitation is also suitable for removing oligomericfractions from thermoplastic resins. (See, for example, Niederauer etal., Bioseparation, Vol. 47, “Advances in BiochemicalEngineering/Biotechnology,” pages 159 to 188, 2006; and Loadman, M. J.R., “Analysis of Rubber and Rubber-Like Polymers,” 4^(th) Ed., SpringerScience and Business Media, B. V., Dordrecht, Netherlands, 1998). Thesolubility in a given solvent depends on its concentration, molecularweight, and the temperature of the solution. Under certain conditions,the thermoplastic resin with a molecular weight above a certain value isnot soluble anymore and precipitates, while the low molecular weightspecies remain soluble. By separating the precipitate from the solutionby filtration or centrifuging, the oligomeric fractions can be removedfrom thermoplastic resins.

Another technique commonly used to separate oligomers from thermoplasticresins is preparative gel permeation chromatography, sometimes referredto in the literature as size exclusion chromatography (SEC) or gelpermeation chromatography. (See, for example, Lesec, J., J. LiquidChrom., 8(5):875-923, 2006; and Striegel, A. et al., “ModernSize-Exclusion Liquid Chromatography: Practice of Gel Permeation and GelFiltration Chromatography,” 2^(nd) Ed., John Wiley & Sons, Inc.,Hoboken, N.J., 2009). This methodology is successfully applied in thepharmaceutical industry to separate and fractionate mixtures. As appliedto thermoplastic resin samples, a solution of the thermoplastic resinsample is applied to the top of a gel column. The gel particles havedistinct pore sizes of a diameter that is in the same range of thethermoplastic resin. The low molecular weight fraction of thethermoplastic resin will diffuse deep into the gel particle pores, whilethe larger molecular weight fractions of the thermoplastic resin canonly diffuse a small distance into the gel. As a consequence, the largersized molecules of thermoplastic resin are less retained then thesmaller sized molecules, resulting in a separation between theoligomeric fraction of the thermoplastic resin and larger thermoplasticresin molecules.

Evaporation (wiped film evaporation) and distillation techniques arewidely used to separate oligomers from thermoplastic resins. (See, forinstance, U.S. Pat. No. 4,160,692). Temperature and pressure areimportant parameters to achieve adequate separation. In addition, theuse of a carrier gas, such as a stream of nitrogen, or stream of steam,can help to improve the separation, but also specific designs ofevaporation/distillation hardware, such as thin film evaporators, ordistillation columns, can enhance the separation. Evaporation hastypically a lower selectivity than distillation and is used when thereis a large difference in boiling point between the distillate andresidue.

Compositions Comprising Modified Thermoplastic Resins and Uses Thereof

The modified thermoplastic resins described above can be incorporatedinto various chemical compositions with numerous applications. Thechemical compositions are, for example, solvent borne, waterborne,emulsions, 100% solids, or hot melt compositions/adhesives. Forinstance, the modified thermoplastic resins can be blended withpolymers. More specifically, in one embodiment, various thermoplasticelastomers, EVAs, various polyolefins, polyesters, acrylics, andacrylates can be blended with the disclosed modified thermoplasticresins. In another embodiment, modified thermoplastic resin compositionsinclude rubber compositions or mixtures comprising various polymers andrubber compounds commonly used in, for example, the tire industry,explained in further detail below. Provided below are severalnon-limiting examples of how the disclosed modified thermoplastic resinscan be incorporated into various products to impart on these productsbeneficial and useful properties not previously available.

Disclosed are modified thermoplastic resins that can be easily blendedwith other polymers as known in the art. As explained above, themodified thermoplastic resins are processed in a manner that decreasesor reduces the amount of low molecular weight species, i.e. dimers,trimers, tetramers, and/or pentamers, from the modified thermoplasticresin as compared with the corresponding unmodified thermoplastic resin.The modified thermoplastic resins therefore possess a lower oligomercontent. The low oligomer content of the modified thermoplastic resinsprovides these modified thermoplastic resins with a better compatibilitywith polymers and a higher glass transition temperature (Tg) toz-average molecular weight (Mz) ratio (Tg/Mz) than is currentlyavailable with similar commercial unmodified thermoplastic resins. Morespecifically, the polymers of interest for modification are typicallythermoplastic elastomers (such as styrene block copolymers), elastomers(such as styrene-butadiene rubber (SBR), butadiene rubber (BR), andnatural rubber), ethylene vinyl acetate (EVA) polymers, variouspolyolefins and alpha-polyolefins, reactor-ready polyolefins,thermoplastic olefins, polyesters, acrylics, and acrylates, filled andunfilled, with and without crosslinking.

The thermoplastic elastomer compositions further optionally includepolyolefins comprising amorphous or crystalline homopolymers orcopolymers of two or more different monomers derived fromalpha-mono-olefins having from 2 to about 12 carbon atoms, or from 2 toabout 8 carbon atoms. Non-limiting examples of suitable olefins includeethylene, propylene, 1-butene, 1-pentene, 1-hexene, 2-methyl-1-propene,3-methyl-1-pentene, 4-methyl-1-pentene, 5-methyl-1-hexene, andcombinations thereof. Additional suitable polyolefins include, but arenot limited to, low density polyethylene, high-density polyethylene,linear-low-density polyethylene, poly-propylene (isotactic andsyndiotactic), ethylene/propylene copolymers, polybutene, and olefinicblock copolymers. Polyolefin copolymers also include the greater part byweight of one or more olefin monomers and a lesser amount of one or morenon-olefin monomers, such as vinyl monomers including vinyl acetate, ora diene monomer, EPDM, and the like. Generally, a polyolefin copolymerincludes less than about 30 weight percent of a non-olefin monomer, lessthan 20 weight percent, or less than about 10 weight percent of anon-olefin monomer. Polyolefin polymers and copolymers are commerciallyavailable from sources including, but not limited to, Chevron, DowChemical, DuPont, Exxon Mobil, REXtac, LLC, Ticona, and Westlake Polymerunder various designations.

Migration and volatilization of low molecular weight components ofcurrently commercially available unmodified thermoplastic resins used tomodify elastomeric compounds such as adhesives, thermoplastic elastomer(TPE) compounds, molding compounds, mastics, etc. causes release ofunpleasant odors, volatiles, fogging, product defects, reduced productcohesive strength, reduced adhesion, degradation of performance overtime, and increased cost by using larger amounts of thermoplastic resinto get the desired change in property provided by the higher molecularweight portion of the thermoplastic resin used.

TPE compositions incorporating the modified resins described herein arein some embodiments formed into a variety of articles as well understoodby those of ordinary skill in the art. For example, TPE compositions arereprocessed, such as by being pressed, compression molded, injectionmolded, calendared, thermoformed, blow-molded, or extruded into finalarticles and embodiments thereof. When reprocessing TPE compositions,the composition is generally heated to a temperature of at least thesoftening or melting point of the thermoplastic component of the TPEcomposition in order to facilitate further forming into desired articlesof various shapes and sizes. The end user of the TPE compositions willbenefit by the processing advantages described throughout thisdisclosure.

Any polymer known in the art can be mixed with the modifiedthermoplastic resins described herein to create compositions useful invarious end products such as adhesives, described herein. For instance,in one embodiment, TPEs include, but are not limited to, blockcopolymers thermoplastic/elastomer blends and alloys, such as styrenicblock copolymers (TPE-S), metallocene-catalyzed polyolefin polymers andelastomers, and reactor-made thermoplastic polyolefin elastomers. Blockcopolymers include, but are not limited to, styrenic block copolymer,olefin block copolymer, co-polyester block copolymer, polyurethane blockcopolymer and polyamide block copolymer. Thermoplastic/elastomer blendsand alloys include, but are not limited to, thermoplastic polyolefinsand thermoplastic vulcanizates. Two-phase TPEs are in some embodimentscombined with the disclosed modified thermoplastic resins in these enduse applications described herein. TPE-S copolymers include, but are notlimited to, styrene-butadiene-styrene block copolymer (SBS),styrene-ethylene/butylene-styrene block copolymer (SEBS),styrene-ethylene-ethylene/propylene-styrene block copolymer (SEEPS), andstyrene-isoprene-styrene block copolymer (SIS).

Use of the modified thermoplastic resins disclosed herein having reducedoligomers will provide better compatibility in elastomeric compounds,increasing or maintaining the desired performance improvements inproperties such as, but not limited to, adhesion, cohesion, dimensionalstability, chemical stability, and heat resistance.

Having a modified thermoplastic resin with an increased Tg/Mz ratio canincrease the change in the desired performance per unit of the modifiedthermoplastic resin added to a composition, such as providing equivalentor better peel adhesion at lower loading of modified thermoplastic resinthan of current commercially available unmodified thermoplastic resin.The reduction in oligomers can reduce out-gassing or volatilization oflow molecular weight components, providing advantages such as reduceddefects due to bubbles, reduced odor, and reduced fogging. The reductionin oligomers/oils of the modified thermoplastic resins can also reducethe possibility of migration of the modified thermoplastic resin into anadjacent material, such as rubber, film, food, etc. This reduces anycontamination issues, and reduced changes in performance of eithermaterial, such as reducing the tendency of an elastomer to becomebrittle due to out-migration of a plasticizing compound.

Tables 3A and 3B present expected performance enhancements fromincorporation of modified thermoplastic resins having a narrow molecularweight distribution, i.e. possessing a relatively reduced amount ofoligomer fraction, i.e. dimers, trimers, tetramers, and/or pentamers,particularly modified thermoplastic resins with little to no monomer,dimer, trimer, and/or pentamer content, in various applications where weenvision these attributes to be advantageous. Upper case “X” indicatedin Tables 3A and 3B indicates which attribute that is achievable by themodified thermoplastic resin disclosed herein and that is desirable ineach application. A brief discussion of the application and appropriatetesting to show improvement follows Tables 3A and 3B.

TABLE 3A Expected Performance Enhancements From Modified ThermoplasticResins Attributes Adhesive Cohesive Heat Reduced volatility, Reducedstrength per strength resistance reduced fogging component phr added perphr added per phr added & out gassing migration ApplicationsThermoplastic X X X X X Elastomer (TPE) compounds Food contact grade X XX X adhesives (plastics directive approval) Pressure sensitive X X X X Xadhesives sealants, caulks X X X X X coupling agents for X X X Xwood-plastic composites low profile additive X X X X for sheet moldingcompounds (SMCs) and dough molding compounds (DMCs) polymeric X X X X Xplasticizers/modifiers for polyvinyl chloride (PVC), etc. filmmodification X X X X X woodworking X X X X X adhesives Disposables, X XX X X nonwovens (Hygiene particularly elastic adhesives) Packaging(rigid, X X X X X e.g. cardboard) Laminating X X X X X adhesives (flexpack, industrial, and the like) Heat seal X X X X X coatings/adhesiveslidding-heat seal X X X X X Rubber X X X X X modification for gaskets,hoses, etc. Investment casting X X X X wax Structural X X X X Xadhesives tackifiers/modifiers X X X X X for polyacrylic blendsCementitious X X X X X adhesives (concrete, mastics, and the like)Textile sizing X X X X X (woven, nonwoven) Automotive X X X X Xcomponents

TABLE 3B Expected Performance Enhancements From Modified ThermoplasticResins Attributes reduced Reduced high Mz Reduced high Mz Reduced odor,taste Dimensional fraction-better fraction-better Faster product effectsstability compatibility aged stability processing defects ApplicationsTPE compounds X X X X X Food contact grade X X X X X adhesives (plasticsdirective approval) Pressure sensitive X X X adhesives sealants, caulksX X X X coupling agents for X X X wood-plastic composites low profileadditive X X X X for SMC (sheet molding compound) and DMC compoundspolymeric X X X X X plasticizers/modifiers for PVC etc. filmmodification X X X X X woodworking X X X X X adhesives Disposables, X XX X X nonwovens (Hygiene particularly elastic adhesives) Packaging(rigid, X X X X X e.g., cardboard) Laminating X X X X X adhesives (flexpack, industrial, etc.) Heat seal X X X X coatings/adhesiveslidding-heat seal X X X X Rubber modification X X X X X for gaskets,hoses, and the like Investment casting X X X X wax Structural adhesivesX X X X tackifiers/modifiers X X X for polyacrylic blends Cementitious XX X X adhesives (concrete, mastics, etc.) Textile sizing X X X (woven,nonwoven) Automotive X X X X components

The modified thermoplastic resins can perform advantageously in thefollowing useful applications. The removal of volatile oligomers wouldespecially benefit products such as low shrinkage sheet molded articlesand dough molded compounds, for example, by reducing the occurrence ofbubbles and other defects in the molded part. Additionally, thedisclosed modified thermoplastic resins can reduce cycle time because ofthe absence of low molecular weight fractions with low glass transitiontemperatures. Also, product appearance can be improved by reduction ofhaze caused by high Mz components present in current commerciallyavailable unmodified thermoplastic resins.

Low profile additives are thermoplastic/elastomeric polymers that areadded to polyester or glass composites during formulation to improvesurface finish and avoid shrinkage. It is known that composites undergohigh volumetric shrinkage during polymerization of unsaturated polyesterthermoplastic resin resulting in poor surface appearance, fiberprominence, warpage of molded parts and internal cracks and voids. Lowprofile additives are typically mixed with unsaturated polyesterthermoplastic resins to prevent shrinkage during polymerization (7% to10% by volume) to conserve its dimensional stability. Duringpolymerization, low profile additives, and unsaturated polyesterthermoplastic resins are in homogeneous liquid phase and with the risein temperature unsaturated polyester thermoplastic resins polymerizecausing expansion of low profile additives. (See, “Low Profile Additives(LPA) Market Analysis by Product (PVA, PMMA, PS, HDPE), by Application(SMC/BMC, Pultrusion, RTM) And Segment Forecasts to 2020” by Grand ViewResearch, Published April 2015, Report ID: 978-1-68038-240-2.

The modified thermoplastic resins disclosed herein can be incorporatedinto compositions for non-migrating plasticizers, for example in PVCextruded articles, or in adhesives in contact with plastics and/orelastomeric compounds into which the low molecular weight components ofthe currently commercially available unmodified thermoplastic resinsproducts would migrate.

The low polydispersity can also provide improved performance at reducedaddition levels (or phr, parts thermoplastic resin per hundred parts ofrubber/elastomer/polymer), as compared with corresponding non-modifiedthermoplastic resins, resulting in a reduced cost product. Additionally,higher levels of performance can be obtained at addition levels equal toor less than current use levels in an application since the narrowpolydispersity can yield improved compatibility/solubility in thecompound/formulation.

Also, the reduced high molecular weight tail of the modifiedthermoplastic resins described herein can improve compatibility withelastomeric, thermoplastic, and composite compositions, improvinglong-term stability of the compounds.

Further, the absence of low Tg components in the modified thermoplasticresins can allow compounds such as packaging adhesives to “set” morequickly, permitting greater formulation flexibility, possibly reducingthe number of packages that fail by opening prematurely, and/or enablingincreased processing speed on packaging lines and reducing cost.Additionally, the reduction in high Mz components of the disclosedmodified thermoplastic resin can provide improved compatibility with theother components of a compound. This improved compatibility can resultin a narrower glass transition of the compound, resulting in faster settimes, lower heat sealing temperatures and/or faster heat sealprocessing.

Thus, the modified thermoplastic resins can be used with advantageousproperties, such as enhancement of flexibility, prevention of stresscracking, improved processability, in many contexts, such as, but notlimited to, hydrogenation for performance enhancers for rubberformulations, nitration for polyacrylic blends, hydrogenation tometallocene polyethylene (m-PE) tackifier applications for adhesives,hydrogenation to SBS tackifier applications for nonwoven adhesives,precision casting for lost-wax precision castings for increaseddimensional stability, polyester applications for low profile additivesin sheet molding compounds (SMCs) and dough molding compounds (DMCs),maleic anhydride additives for fiberglass reinforced plastics, as anadditive for expanded polystyrene and lightweight concrete, ascellulosic fillers for coupling agents for wood-plastic compositematerials, and in combination with plasticizers for non-migratingpolymeric plasticizers for polyvinyl chloride (PVC) extrusions, and thelike.

Disposable hygiene articles comprising an adhesive comprising themodified thermoplastic resins can exhibit improved adhesive strength andcohesive strength by improved values in peel adhesion testing of thelaminate construction, improved peel adhesion after aging at bodytemperature, reduced creep of elastic strands over time, and improvedcore stability in a final hygiene article. Said articles may alsoexhibit improves chemical resistance and barrier properties,particularly regarding exposure to fluids such as body fluids.

Adhesives useful in packaging, product assembly, woodworking, automotiveassembly and other applications, which are based on ethylene vinylacetate, ethylene-butyl-acrylate, acrylics, semi-crystalline single-sitecatalyzed (metallocene) polyolefins, predominantly amorphous polyalpha-olefins such as Ziegler-Natta catalyzed polymers, reactor-readypolyolefins, thermoplastic olefins, and styrene block copolymers wouldexhibit improved adhesive and cohesive strength as measured by peeladhesion failure temperature (PAFT) testing, fiber tear testing, peeltesting on adhered structures, shear adhesion failure temperature (SAFT)testing, IoPP (Institute of Packaging Professionals, Naperville, Ill.,US) test T-3006 Heat Stress Resistance of Hot Melt Adhesives, and shearhold power. Set times can be measured using various bond testers withadjustable compression and de-bonding times. Said adhesives comprisingthe modified thermoplastic resin would exhibit improved heat resistanceas evidenced by fiber tear or peel adhesion testing at elevatedtemperatures such as 60° C. Improved chemical resistance may be shown byreduced degradation of adhesive and cohesive strength after exposure toselected chemicals. More detailed description of adhesive applicationsof the modified thermoplastic resins described herein is provided below.

Non-vulcanized compositions comprising the modified thermoplastic resinsdisclosed herein can act as superior plasticizers or can improveplasticizer performance by reducing migration, as evidenced to improvedadhesion over time, particularly after heat aging, as evidenced by anyof the test methods above: PAFT, SAFT, peel, fiber tear, shear holdpower at and above room temperature. Similarly, said compositions mayexhibit improved adhesion to difficult surfaces or to substrates withmigratory components (e.g. slip aids or plasticizers), as evidenced bythe above listed adhesion tests.

Investment casing wax compositions comprising the disclosed modifiedthermoplastic resins can exhibit improved rheology for consistentproduction of parts, as evidenced by the composition rheology(stress-strain curves). Improved dimensional stability of the waxcasting composition and improved casting composition stability duringmold making are evidenced by improved tolerances on the cast product.

Heat seal coatings and adhesives can exhibit heat resistance by improvedpeel adhesion testing at temperatures near and above the sealingtemperatures using ASTM F88.

Sealants can exhibit reduced fogging of sealed windows after aging.

The improved structural stability of sealants and gaskets and otherrubber-based materials can be evidenced by improved dimensionalstability following compression or elongation.

Vibration and sound damping improvement can be measured by ASTM E756 forsealants, gaskets, structural adhesives, cementitious, bitumen, andasphalt adhesives, thermoplastic elastomer (TPE) compounds and pressuresensitives.

Mastics containing bitumen, asphalt, or similar materials can have lowerviscosity than current compositions, allowing easier processing, whileexhibiting comparable or better adhesion to aggregate components,fillers, and substrates such as stone or cement, as evidenced by tensiletesting on adhered stone or cement samples. Such mastics findapplication in the production of bridge decking, flooring, roadconstruction, and roofing.

Reduction of low molecular components in compositions, particularly foodpackaging adhesives, can be measured by recent tests being used tomeasure mineral oil content at Fraunhofer Institute in Germany, asfollows:

MOSH=Mineral oil saturated hydrocarbons

MOAH=Mineral oil aromatic hydrocarbons

Reduction of low molecular weight components in compositions such aspressure sensitive adhesives (tape, label, graphics protective films,window film) can provide performance improvements measured by, forexample:

Adhesive strength: 180 degree peel test, e.g., PSTC 101.

Cohesive strength: static shear test (room temp. or elevated temp.),e.g., PSTC 107.

Temperature resistance: shear adhesion failure temperature (SAFT), e.g.,PSTC 17 or AFERA 5013 GTF 6001.

Reduction of low molecular components in thermoplastic elastomers (TPEs)can provide performance improvements measured by, for example:

Cohesive strength: tensile (ASTM 638), and tear (ASTM D624).

Compression set (elasticity) ASTM 395-15

Temperature resistance: elevated temperature tensile and tear strength,and elevated temperature compression set (ASTM 395-15).

Performance improvements resulting from reduced low molecular weightcomponents in the modified resin in various composites can be measuredusing, for example:

Standard Guide for Testing Polymer Matrix Composite Materials (ASTMD4762-16);

Standard Test Method for Tensile Properties of Polymer Matrix CompositeMaterials (ASTM D3039/D3039M-14); and

Standard Test Method for Glass Transition Temperature (DMA Tg) ofPolymer Matrix Composites by Dynamic Mechanical Analysis (DMA) (ASTMD7028-07(2015)).

In general resistance to solvents, water, foods, cleaning products, andother chemicals can be measured by direct exposure up to and includingimmersion for a period of time followed by testing above to compare topristine material testing. Visual observations are made in general fordegradation of articles during/after exposure. Uptake of the test fluidcan be measured gravimetrically or spectroscopically.

Barrier properties are tested in specialized equipment to measure theflow rate of gases, water vapor, fluids, and the like, through a film ofmaterial.

Compatibility with fillers can be discerned indirectly via improvedmechanical properties relative to controls. Also, it is typical toevaluate with various microscopic techniques the type and degree ofdispersion of the filler.

One problem associated with pressure-sensitive adhesives (PSAs) based ontackified elastomeric blends is diffusion and migration of tackifiersand other species from the adhesive composition or article componentsinto the facestock or substrate. As a result, the facestock or substratemay become stained over time and the construction may lose someadhesion. This migration or bleed through of some or all components ofan adhesive, compounded film, or other composition comprisingthermoplastic resins can also leave a residue on the bonded surface uponremoval, such as with protective films, or can cause undesired surfacecontamination, skin irritation, etc. More critical to adhesiveapplications, compounds comprising thermoplastic resins or multilayerfilms, the migration or “bleed through” of chemical components towardsthe bonded interfaces, e.g. adhesive-substrate orfilm-adhesive-nonwoven, can cause immediate or delayed reduction orelimination of bond strength, damage to the bonded or laminated article,and/or reduction of adhesion with aging.

U.S. Pat. No. 6,214,935 describes the use of an intermediate softeningpoint resins having a ring and ball softening point of from about 35° C.to 60° C. and an aromatic content of from about 5% to 25% as a method toreduce bleed through and staining of label facestock paper due totackifier components, but handling such semi-solid, highly viscousresins that cold flow over time is very challenging and costly. Thus,there is a need for thermoplastic resins for use in adhesives that canbe used alone or in combination with other thermoplastic resins and thatexhibit reduced volatile components, fog generation, and migration.

The aforementioned compositions comprising the modified thermoplasticresins in some embodiments further comprise at least one polymer andabout 0 to about 75 wt % un-modified thermoplastic tackifying resin. Inanother embodiment, the adhesive composition comprises at least onethermoplastic elastomer and at least one thermoplastic resin, inaddition to the modified thermoplastic resin. The thermoplasticelastomer can, for instance be one or more of hydrogenated and/ornonhydrogenated styrenic block copolymers including, but not limited to,styrene-butadiene-styrene block copolymer (SBS),styrene-ethylene/butylene-styrene block copolymer (SEBS),styrene-[ethylene-(ethylene/propylene)]-styrene block copolymer (SEEPS),and/or styrene-isoprene-styrene block copolymer (SIS). In anotherembodiment, the adhesive compositions described herein exhibit aviscosity at 177° C. of about 50 to about 10,000 cP, and a softeningpoint of about 60 to about 180° C. and are suitable adhesives.

In the composition embodiments described herein, the adhesivecompositions can comprise at least 1, 2, 3, 4, 5, 10, 15, 20, 25, 30,35, 40, 45, 50, 55, or 60 and/or not more than 99, 95, 90, 85, 80, 75,70, or 65 weight percent of at least one modified thermoplastic resin.

In various embodiments, the compositions comprise 10, 20, 30, or 40and/or not more than 90, 80, 70, or 55 weight percent of at least onepolymer component. Exemplary polymer components of the disclosedcompositions include, but are not limited to, ethylene vinyl acetatecopolymer, ethylene n-butyl acrylate copolymer, ethylene methyl acrylatecopolymer, polyester, neoprene, acrylics, urethane, poly(acrylate),ethylene acrylic acid copolymer, polyether ether ketone, polyamide,styrenic block copolymers, random styrenic copolymers, hydrogenatedstyrenic block copolymers, styrene butadiene copolymers, natural rubber,polyisoprene, polyisobutylene, atactic polypropylene, polyethyleneincluding atactic polypropylene, ethylene-propylene polymers,propylene-hexene polymers, ethylene-butene polymers, ethylene octenepolymers, propylene-butene polymers, propylene-octene polymers,metallocene-catalyzed polypropylene polymers, metallocene-catalyzedpolyethylene polymers, ethylene-propylene-butylene terpolymers,copolymers produced from propylene, ethylene, and various C₄-C₁₀alpha-olefin monomers, polypropylene polymers, functional polymers suchas maleated polyolefins, butyl rubber, polyester copolymers, copolyesterpolymers, isoprene, the terpolymer formed from the monomers ethylene,propylene, and a bicyclic olefin (known as “EPDM”), isoprene-based blockcopolymers, butadiene-based block copolymers, acrylate copolymers suchas ethylene acrylic acid copolymer, butadiene acrylonitrile rubber,and/or polyvinyl acetate.

The compositions disclosed herein, in various embodiments, containelastomer, tackifier resin, and other additives such as, but not limitedto, oils, waxes, plasticizers, antioxidants, and fillers, depending onthe end use application. In various embodiments, the compositionscomprise at least about 5, 10, 15, 20, 25, 30, 35, 40, 45, or 50, and/ornot more than 500, 450, 400, 350, or 300 parts of elastomer, tackifierresin, and/or other additives per 100 parts of modified thermoplasticresin. For example, in one embodiment, the compositions disclosed hereincontain about 50 to about 300 parts of elastomer per 100 parts ofmodified thermoplastic resin.

As noted above, in some embodiments, the described compositions compriseadditives particularly suitable for a specific end-use application. Forexample, if the adhesive is intended to serve as a hot melt packagingadhesive, as noted above, then in this embodiment, the composition willfurther comprise a wax. In some embodiments, the adhesive compositioncomprises at least 1, 2, 5, 8, or 10 and/or not more than 40, 30, 25, or20 weight percent of at least one wax. In another embodiment, thecompositions described herein comprise about 1 to about 40, about 5 toabout 30, about 8 to about 25, or about 10 to about 20 weight percent ofat least one wax. Suitable waxes include, without limitation,microcrystalline wax, paraffin wax, waxes produced by Fischer-Tropschprocesses, vegetable wax, functionalized waxes (maleated, fumerated, orwax with functional groups), and the like. In such embodiments, a wax isincluded in the composition in an amount of between about 10 and about100 parts wax per 100 parts of the elastomer component.

In pressure sensitive adhesive (PSA) composition embodiments, such asadhesives used in tapes, mastics, and labels, and in nonwovenapplications of the described adhesive compositions, various oils areadded to the adhesive compositions. In one embodiment, the adhesivecomposition comprises at least about 1, 2, 5, 8, or about 10 and/or notmore than about 40, 30, 25, or about 20 weight percent of at least oneprocessing oil. In another embodiment of pressure sensitive adhesivecompositions, the adhesive compositions comprise about 2 to about 40,about 5 to about 30, about 8 to about 25, or about 10 to about 20 weightpercent of at least one processing oil. Processing oils include, but arenot limited to, mineral oils, naphthenic oils, paraffinic oils, aromaticoils, castor oils, rape seed oil, triglyceride oils, and combinationsthereof. Processing oils also include extender oils that are commonlyused in various pressure-sensitive adhesive compositions. In anotherembodiment, the described adhesive composition comprises no processingoils.

In another embodiment of the compositions, one or more plasticizers areadded to the adhesive compositions, such as, but not limited to,phthalate esters such as, for example, dibutyl phthalate and dioctylphthalate, benzoates, terephthalates, and chlorinated paraffins. In oneembodiment, the described adhesive compositions comprise at least about0.5, 1, 2, or about 3 and/or not more than about 20, 10, 8, or about 5weight percent of at least one plasticizer. In another embodiment, theadhesive compositions comprise about 0.5 to about 20, about 1 to about10, about 2 to about 8, or about 3 to about 5 weight percent of at leastone plasticizer. Other exemplary plasticizers include Benzoflex™ andEastman 168™ (Eastman Chemical Company, Kingsport, Tenn., US).

In other embodiments, the compositions that incorporate one or moremodified resins further comprise at least about 0.1, 0.5, 1, 2, or about3 and/or not more than about 20, 10, 8, or about 5 weight percent of atleast one antioxidant. Any antioxidant known to a person of ordinaryskill in the art may be used in the adhesion compositions disclosedherein. Non-limiting examples of suitable antioxidants includeamine-based antioxidants such as alkyl diphenyl amines,phenyl-naphthylamine, alkyl or aralkyl substituted phenyl-naphthylamine,alkylated p-phenylene diamines, tetramethyl-diaminodiphenylamine and thelike; and hindered phenol compounds such as2,6-di-t-butyl-4-methylphenol;1,3,5-trimethyl-2,4,6-tris(3′,5′-di-t-butyl-4′-hydroxybenzyl)benzene;tetra kis [(methylene(3,5-di-t-butyl-4-hydroxyhydrocinnamate)] methane,such as IRGANOX® 1010 (BASF Corp., LA, US);octadecyl-3,5-di-t-butyl-4-hydroxycinnamate, such as IRGANOX® 1076 (BASFCorp., LA, US) and combinations thereof. Where used, the amount of theantioxidant in the composition can be from about greater than 0 to about1 wt %, from about 0.05 to about 0.75 wt %, or from about 0.1 to about0.5 wt % of the total weight of the composition. In another suchembodiment, the adhesive compositions comprise about 0.1 to about 20,about 1 to about 10, about 2 to about 8, or about 3 to about 5 weightpercent of at least one antioxidant.

In another embodiment of the compositions, the composition comprises oneor more fillers, such as, but not limited to, carbon black, calciumcarbonate, titanium oxide, and zinc oxide. In another embodiment of thedescribed compositions, the compositions comprise at least about 10, 20,30, or about 40 and/or not more than about 90, 80, 70, or about 55weight percent of at least one filler. In a further embodiment, thecompositions comprise about 1 to about 90, about 20 to about 80, about30 to about 70, or about 40 to about 55 weight percent of at least onefiller.

Additionally, other tackifier resins are present in various embodimentsof the described compositions, which are optionally present in the formof physical blends. Tackifier resins added to the described compositionsin this embodiment include, without limitation, cycloaliphatichydrocarbon resins, C₅ hydrocarbon resins, C₅/C₉ hydrocarbon resins,aromatically modified C₅ resins, C₉ hydrocarbon resins, pure monomerresins, e.g., copolymers of styrene with alpha-methyl styrene, vinyltoluene, para-methyl styrene, indene, and methyl indene, DCPD resins,dicyclopentadiene based/containing resins, cyclo-pentadienebased/containing resins, terpene resins, terpene phenolic resins,terpene styrene resins, esters of rosin, esters of modified rosins,liquid resins of fully or partially hydrogenated rosins, fully orpartially hydrogenated rosin esters, fully or partially hydrogenatedmodified rosins resins, fully or partially rosin alcohols, fully orpartially hydrogenated C₅ resins, fully or partially hydrogenated C₅/C₉resins, fully or partially hydrogenated DCPD resins, fully or partiallyhydrogenated dicyclopentadiene based/containing resins, fully orpartially hydrogenated cyclo-pentadiene based/containing resins, fullyor partially hydrogenated aromatically modified C₅ resins, fully orpartially hydrogenated C9 resins, fully or partially hydrogenated puremonomer resins, e.g., copolymers or styrene with alpha-methyl styrene,vinyl toluene, para-methyl styrene, indene, and methyl indene, fully orpartially hydrogenated C₅/cycloaliphatic resins, fully or partiallyhydrogenated C₅/cycloaliphatic/styrene/C₉ resins, fully or partiallyhydrogenated cycloaliphatic resins, and mixtures thereof.

In some embodiments, the compositions described herein include otherconventional plastic additives in an amount that is sufficient to obtaina desired processing or performance property for the adhesive. Theamount should not be wasteful of the additive nor detrimental to theprocessing or performance of the adhesive. Those skilled in the art ofthermoplastics compounding, without undue experimentation but withreference to such treatises as Plastics Additives Database (2004) fromPlastics Design Library (www.elsevier.com) can select from manydifferent types of additives for inclusion into the compounds describedherein. Non-limiting examples of optional additives include adhesionpromoters; biocides (antibacterials, fungicides, and mildewcides),anti-fogging agents; anti-static agents; bonding, blowing and foamingagents; dispersants; fillers and extenders; fire and flame retardantsand smoke suppressants; impact modifiers; initiators; lubricants; micas;pigments, colorants and dyes; oils and plasticizers; processing aids;release agents; silanes, titanates and zirconates; slip andanti-blocking agents; stabilizers (for example, Irganox® 1010 andIrganox® 1076, BASF Corporation, LA, US); stearates; ultraviolet lightabsorbers; viscosity regulators; waxes; and combinations thereof.Antioxidants are particularly useful for these compounds to provideadditional durability.

Such compositions are manufactured in one embodiment by blending themodified thermoplastic resin with an elastomer (at least one polymer) toform the adhesive. That is, the adhesive compositions described hereinare in one embodiment prepared by combining the modified thermoplasticresin, the elastomer, and the additives using conventional techniquesand equipment. As a non-limiting exemplary embodiment, the components ofthe compositions described herein are blended in a mixer such as a Sigmablade mixer, a plasticorder, a Brabender mixer, a twin-screw extruder,and/or an in-can blend can (pint-cans). In another embodiment, thecompositions are shaped into a desired form, such as a tape or sheet, byan appropriate technique including, for example, extrusion, compressionmolding, calendaring, or roll coating techniques (gravure, reverse roll,and the like). In some embodiments, the compositions described hereinare applied using curtain coating, slot-die coating, or sprayed throughdifferent nozzle configurations at different speeds using typicalapplication equipment.

In another embodiment, the compositions described herein are applied toa substrate by melting the composition and then using conventional hotmelt adhesive application equipment recognized in the art to coat thesubstrate with the composition. Substrates include, for example,textile, fabric, paper, glass, plastic, and metal materials. Typically,about 0.1 to about 100 g/m² of adhesive composition is applied to asubstrate.

The modified thermoplastic resins described herein, in some embodiments,are incorporated into various types of compositions including, but notlimited to, hot melt or solvent based pressure sensitive adhesives,e.g., tapes, labels, mastics, HVACs, and the like, hot melt nonwovenadhesives, e.g., those for use in the construction industry, for elasticattachment, or for stretching, and hot melt packaging adhesives.Furthermore, the modified thermoplastic resins described herein inanother embodiment are incorporated into different polymer systems asexplained above to provide excellent physical and chemical properties interms of processability, stability, thermal properties, viscoelasticity,rheology, volatility, fogging profiles, and/or adhesion and mechanicalproperties of such polymer systems. Moreover, the modified thermoplasticresins described herein enhance various physical and chemical propertiesin thermoplastic elastomer applications such as roofing applications(construction), adhesives, sealant applications, cable flooding/fillingapplications, and tire elastomer applications, e.g., tread compositions,side walls, inner liners, inner-tubes, and various other pneumatic tirecomponents, for example.

While the preceding discussion is primarily directed to adhesiveapplications incorporating the modified thermoplastic resins describedherein, these principals can be generally expanded and applied to otherthermoelastic polymer compositions comprising the modified thermoplasticresins for use in a myriad number of end products. For instance, polymermodification applications for thermoplastic elastomers incorporating themodified thermoplastic resins described herein include, but are notlimited to, roofing applications (such as asphalt modifiers in modifiedbitumen roofing), water proofing membranes/compounds, underlayments,cable flooding/filling compounds, caulks and sealants, polymercompounds/blends, films, e.g., cling films, TPE films, BiaxiallyOriented PolyPropylene (BOPP) films, and the like, molded articles,rubber additive/processing aids, carpet backing, e.g., high performanceprecoat, thermoplastic compound, and the like, wire and cables, powerand hand tools, pen grips, airbag covers, grips and handles, seals, andlaminated articles, e.g., paper lamination, water activated, hot meltgummed, scrim reinforced tape, and the like. When incorporated intothese various end use applications, the described modified thermoplasticresins in some embodiments are the sole resin in the compositions. Inother embodiments, the modified thermoplastic resins are combined withother resins, elastomers/polymers, and/or additives. In such combinedresin applications, the aforementioned compositions comprise at leastabout 1, 2, 3, 4, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, or about 60and/or not more than about 99, 95, 90, 85, 80, 75, 70, or about 65weight percent of at least one modified thermoplastic resin.

Thus, in various embodiments, one or more of the modified thermoplasticresins described herein are incorporated into hot melt adhesivecompositions. According to one or more embodiments, the adhesivestherefore comprise at least about 1, 5, 10, 20, 30, 40, 50, or 60 and/ornot more than about 95, 90, 80, 70, or 60 weight percent (wt %) of themodified thermoplastic resins, or mixtures thereof. Moreover, theadhesives in other embodiments comprise in the range of about 1 to 95, 5to 90, 10 to 80, 20 to 70, 30 to 60, or 40 to 60 weight percent of themodified thermoplastic resins described herein, or mixtures thereof. Incertain additional embodiments, the adhesives are entirely comprised ofone or more the modified thermoplastic resins described herein.Furthermore, depending on the desired end use, these hot melt adhesivesalso comprise, in certain embodiments, various additives such as, forexample, polymers, tackifiers, processing oils, waxes, antioxidants,plasticizers, pigments, and/or fillers.

In various embodiments, the adhesives comprise at least about 5, 10, 20,30, or 40 and/or not more than about 95, 90, 80, 70, or 55 weightpercent of at least one resin that is different from the modifiedthermoplastic resins described herein. Moreover, the adhesives comprise,in other embodiments, in the range of about 10 to 90, 20 to 80, 30 to70, or 40 to 55 weight percent of at least one resin that is differentfrom the modified thermoplastic resins described herein. Contemplatedresins include any suitable resin listed hereinabove.

In various embodiments, the adhesives comprise at least about 10, 20,30, 40, 50, or 60 and/or not more than about 90, 80, 70, or 60 weightpercent of at least one tackifier. Moreover, the adhesives comprise insuch embodiments in the range of about 10 to 90, 20 to 80, 30 to 70, orabout 40 to 60 weight percent of at least one tackifer. Suitabletackifiers contemplated herein include, for example, cycloaliphatichydrocarbon resins, C5 hydrocarbon resins; C5/C9 hydrocarbon resins;aromatically-modified C5 resins; C9 hydrocarbon resins; pure monomerresins such as copolymers of styrene with alpha-methyl styrene, vinyltoluene, para-methyl styrene, indene, methyl indene, C5 resins, and C9resins; terpene resins; terpene phenolic resins; terpene styrene resins;rosin esters; modified rosin esters; liquid resins of fully or partiallyhydrogenated rosins; fully or partially hydrogenated rosin esters; fullyor partially hydrogenated modified rosin resins; fully or partiallyhydrogenated rosin alcohols; fully or partially hydrogenated C5 resins;fully or partially hydrogenated C5/C9 resins; fully or partiallyhydrogenated aromatically-modified C5 resins; fully or partiallyhydrogenated C9 resins; fully or partially hydrogenated pure monomerresins; fully or partially hydrogenated C5/cycloaliphatic resins; fullyor partially hydrogenated C5/cycloaliphatic/styrene/C9 resins; fully orpartially hydrogenated cycloaliphatic resins; and combinations thereof.Exemplary commercial hydrocarbon resins include Regalite™ hydrocarbonresins (Eastman Chemical Co., Kingsport, Tenn., US).

In various embodiments, the adhesives comprise at least about 1, 2, 5,8, or 10 and/or not more than about 40, 30, 25, or 20 weight percent ofat least one processing oil. Moreover, in such embodiments, theadhesives comprise in the range of about 2 to 40, 5 to 30, 8 to 25, orabout 10 to 20 weight percent of at least one processing oil. Suitableprocessing oils are those known in the art, and include, for example,mineral oils, naphthenic oils, paraffinic oils, aromatic oils, castoroils, rape seed oil, triglyceride oils, or combinations thereof. As oneskilled in the art would appreciate, processing oils may also includeextender oils, which are commonly used in adhesives. The use of oils inthe adhesives are in some instances desirable if the adhesive is to beused as a pressure-sensitive adhesive (PSA) to produce tapes or labelsor as an adhesive to adhere nonwoven articles. In certain additionalembodiments, the adhesive comprises no processing oils.

In various embodiments, the adhesives comprise at least about 1, 2, 5,8, or 10 and/or not more than about 40, 30, 25, or 20 weight percent ofat least one wax. Moreover, in such embodiments, the adhesives comprisein the range of about 1 to 40, 5 to 30, 8 to 25, or 10 to 20 weightpercent of at least one wax. Suitable waxes can include those known inthe art, for example, microcrystalline wax, paraffin wax, waxes producedby Fischer-Tropsch processes, functionalized waxes (maleated, fumerated,or wax with functional groups etc.) and vegetable wax. The use of waxesin the adhesives are desirable in certain instances if the adhesive isto be used as a hot melt packaging adhesive. In certain embodiments, theadhesive comprises no wax.

In various embodiments, the adhesives comprise at least about 0.1, 0.5,1, 2, or 3 and/or not more than about 20, 10, 8, or 5 weight percent ofat least one antioxidant. Moreover, in such embodiments, the adhesivescomprise in the range of about 0.1 to 20, 1 to 10, 2 to 8, or 3 to 5weight percent of at least one antioxidant. In other embodiments, theadhesive contains no antioxidant.

In various embodiments, the adhesives comprise at least about 0.5, 1, 2,or 3 and/or not more than about 20, 10, 8, or 5 weight percent of atleast one plasticizer. Moreover, in such embodiments, the adhesivescomprise in the range of about 0.5 to 20, 1 to 10, 2 to 8, or 3 to 5weight percent of at least one plasticizer. Suitable plasticizers arethose known in the art, and include, for example, dibutyl phthalate,dioctyl phthalate, chlorinated paraffins, and phthalate-freeplasticizers. Commercial plasticizers include, for example, Benzoflex™and Eastman 168™ plasticizers (Eastman Chemical Co., Kingsport, Tenn.,US).

In various additional embodiments, the adhesives comprise at least about10, 20, 30, or 40 and/or not more than about 90, 80, 70, or 55 weightpercent of at least one filler. Moreover, in such embodiments, theadhesives comprise in the range of about 1 to 90, 20 to 80, 30 to 70, or40 to 55 weight percent of at least one filler. Suitable fillers arethose known in the art and include, for example, carbon black, calciumcarbonate, titanium oxide, zinc oxide, or combinations thereof.

In another embodiment, a non-vulcanized composition comprising themodified thermoplastic resin comprises about 10 to about 90 weightpercent of at least one polymer, about 5 to about 70 weight percent ofat least one modified thermoplastic resin, about 0 to about 60 weightpercent of at least one thermoplastic tackifying resin, about 0 to about50 weight percent of at least one wax, about 0 to about 60 weightpercent of at least one oil or plasticizer, about 0.5 to about 3 weightpercent of at least one stabilizer, and about 0 to about 70 weightpercent of at least one filler. Alternatively, such compositionscomprise about 40 to about 90 weight percent of at least one polymer,about 10 to about 60 weight percent of at least one modifiedthermoplastic resin, about 0 to about 50 weight percent of at least onethermoplastic tackifying resin, about 0 to about 30 weight percent of atleast one wax, and about 0 to about 20 weight percent of at least oneoil or plasticizer. Alternatively, such embodiments, which are pressuresensitive adhesive embodiments, comprise about 15 to about 70 weightpercent, or about 35 or 40 to about 55 weight percent, of the polymer,wherein greater than about 15 weight percent of the at least one polymeris an elastomeric polymer, about 35 to about 70 weight percent of themodified thermoplastic resin, about 0 to about 50 weight percent of theat least one thermoplastic tackifying resin, and about 5 to about 35weight percent of the at least one oil or plasticizer. In another suchembodiment, the composition comprises about 10 to about 80 weightpercent of the at least one polymer, wherein the at least one polymer isan elastomer, about 5 to about 20 weight percent of the at least onethermoplastic polymer, wherein the thermoplastic polymer is a polyolefinpolymer or copolymer, about 5 to about 25 weight percent of the modifiedthermoplastic resin, about 0 to about 15 weight percent of at least onethermoplastic tackifying resin, about 2 to about 60 weight percent of atleast one oil or plasticizer, and about 10 to about 70 weight percent ofat least one filler. In another embodiment of the non-vulcanizedcompositions comprising the modified thermoplastic resins describedherein comprise about 40 to about 90 weight percent of the at least onepolymer, about 10 to about 60 weight percent of the at least onemodified thermoplastic resin, about 0 to about 50 weight percent of theat least one thermoplastic tackifying resin, about 0 to about 30 weightpercent of the at least one wax, and about 0 to about 20 weight percentof the at least one oil or plasticizer.

In such embodiments, the at least one modified thermoplastic resin has aglass transition temperature (Tg) of between −50° C. and 160° C. In suchembodiments, the modified thermoplastic resin additionally possesses theproperties set forth in Formula I, above, wherein the value of S isgreater than or equal to 2 and less than 50,000 when Oligomer isdetermined by GPC, or greater than or equal to 5 and less than 10,000when Oligomer is determined by high resolution TGA; and wherein thevalue of Mz is less than or equal to 9,000 g/mol. Alternatively, oradditionally, in such embodiments, the modified thermoplastic resin hasa glass transition temperature (Tg) of between −50° C. and 160° C. and anumber average (Mn) molecular weight of less than 3,000 g/mol.Additionally, or alternatively, in this embodiment the modifiedthermoplastic resin has a z-average molecular weight (Mz) of less than9,000 g/mol and the modified thermoplastic resin comprises less than orequal to 38 wt % oligomers as measured by the high resolution thermalgravimetric analysis (TGA), or less than 55% oligomers of equal to orless than 600 g/mol as measured by GPC.

Rubber Compositions Comprising Modified Thermoplastic Resins

Disclosed are rubber compositions for use in, for example, automotivecomponents, such as, but not limited to, tires and tire components,automotive belts, hoses, brakes, and the like, as well as non-automotiveand/or mechanical devices including technical rubber articles such as,for example, belts, as in conveyor belts, for instance, straps, brakes,and hoses or tubing, and the like, as well as clothing articles, suchas, but not limited to, shoes, boots, slippers, and the like, thatincorporate the disclosed modified thermoplastic resins.

Thus, rubber compositions are disclosed that comprise elastomers,fillers, and the modified thermoplastic resins disclosed herein. In oneembodiment, the elastomers are one or more of a natural rubber, apolyisoprene, a styrene-butadiene rubber, a polybutadiene, a halobutylrubber, and a nitrile rubber, or a modified rubber grade, or a rubbermixture thereof. In another embodiment, the halobutyl rubber isbromobutyl rubber, chlorobutyl rubber, a modified rubber grade, or amixture thereof. When used in tire embodiments, the main rubbercomponents of such tire embodiments comprise various polymers such as,but not limited to, polyisoprene (synthetic or natural),styrene-butadiene copolymer, or butadiene polymer, and the like. Inother embodiments, such rubber polymer(s) contain various modificationsand/or functionalizations at the end of chains or at pendant positionsalong the polymer chain. In these embodiments, such modificationscontain various standard moieties such as, but not limited to, hydroxyl-and/or ethoxy- and/or epoxy- and/or siloxane- and/or amine- and/oraminesiloxane- and/or carboxy- and/or phthalocyanine- and/orsilane-sulfide-groups, and/or combinations thereof. Additionalmodifications known to one of skill, such as metal atoms, are alsocontemplated as being included in the rubber polymers used to make thedisclosed tires and other rubber-containing components disclosed herein.

In some embodiments, the rubber mixture according to the disclosure alsocontains 5 to 80 phr, 5 to 49 phr, 5 to 30 phr, or 5 to 20 phr of atleast one further diene rubber.

The at least one further rubber is in this case one or more of naturalpolyisoprene and/or synthetic polyisoprene and/or butadiene rubberand/or solution-polymerized styrene-butadiene rubber and/oremulsion-polymerized styrene-butadiene rubber and/or liquid rubbers witha molecular weight Mw greater than 20,000 g/mol and/or halobutyl rubberand/or polynorbonene and/or isoprene-isobutylene copolymer and/orethylene-propylene-diene rubber and/or nitrile rubber and/or chloroprenerubber and/or acrylate rubber and/or fluorine rubber and/or siliconerubber and/or polysulfide rubber and/or epichlorohydrin rubber and/orstyrene-isoprene-butadiene terpolymer and/or hydrated acrylonitrilebutadiene rubber and/or isoprene-butadiene copolymer and/or hydrogenatedstyrene-butadiene rubber.

In one embodiment, nitrile rubber, hydrogenated acrylonitrile butadienerubber, chloroprene rubber, butyl rubber, halobutyl rubber,ethylene-propylene-diene rubber, or a mixture thereof, is used in theproduction of technical rubber articles such as straps, belts, andhoses, for example.

In another embodiment, the further diene rubber is one or more ofsynthetic polyisoprene and natural polyisoprene and polybutadiene. In afurther embodiment, the further diene rubber is at least naturalpolyisoprene. This allows to achieve particularly favorableprocessability (extrudability, miscibility, et cetera) of the rubbermixture.

According to a further embodiment of the disclosure, the rubber mixturecontains 10 to 70 phr of a conventional solution-polymerizedstyrene-butadiene rubber having a glass transition temperature of −40 to+10° C. (high-Tg SSBR) and 10 to 70 phr of the styrene-butadiene rubberhaving a Tg of −120 to −75° C., −110 to −75° C., −110 to −80° C., or −87to −80° C., with the rubber in this embodiment having a styrene contentof 1 to 12 wt %, 9 to 11 wt %, or 10 to 11 wt %.

In some embodiments, rubber mixture contains at least one further dienerubber, such as a natural and/or synthetic polyisoprene.

The modified thermoplastic resins are incorporated into the rubbermixtures by various methods known to one of skill. The amount ofmodified thermoplastic resin in the rubber mixture is from 5 to 150 phr,5 to 120 phr, or even 5 to 100 phr. The rubber mixture additionallycomprises in some embodiments unmodified thermoplastic resins. Further,mixtures of modified and unmodified thermoplastic resins areincorporated into the rubber mixtures in these embodiments. The totalthermoplastic resin content, including unmodified thermoplastic resinand modified thermoplastic resin, in these embodiments is from 5 to 200phr, 5 to 150 phr, or even 5 to 100 phr, i.e. a modified thermoplasticresin is incorporated into the rubber mixtures to achieve a phr value of5 to 50 by dilution. Likewise, mixtures of modified thermoplastic resinsare in some embodiments incorporated into the rubber mixtures by addingthe desired amount to the rubber mixture to achieve the desired phr.

According to another embodiment, the amount of the solution-polymerizedstyrene-butadiene rubber present in the rubber mixture is from 5 to 50phr, 20 to 50 phr, or even 30 to 40 phr. The rubber mixture of thedisclosure comprises about 20 to 250 phr, 30 to 150 phr, or 30 to 85phr, of at least one filler. The filler is one or more of a polar ornon-polar filler, such as, but not limited to, silica, carbon black,alumino-silicates, chalk, starch, magnesium oxide, titanium dioxide,and/or rubber gels, or mixtures thereof. Further, carbon nanotubes(CNTs) including hollow carbon fibers (HCF) and modified CNTs, includingone or more functional groups such as, for example, hydroxy, carboxy, orcarbonyl groups, are used as filler materials in some embodiments.Additionally, graphite and graphene, as well as “carbon-silicadual-phase filler” are used as filler materials in other embodiments. Itis contemplated herein to use any of the types of carbon black known toa person skilled in the art.

In some embodiments, the rubber mixture comprises carbon black as solefiller or as main filler, that is, the amount of carbon black ismarkedly greater than the amount of any other fillers present. Ifanother filler is present alongside carbon black, in one embodiment theother filler is silica. Thus, in another embodiment, the rubber mixturesdescribed herein comprise similar amounts of carbon black and silica,for example 20 to 100 phr of carbon black combined with 20 to 100 phr ofsilica. For example, the ratio of carbon black to silica can be anywherefrom about 1:150 to 100:20.

In some embodiments, the rubber mixture comprises silica as sole filleror as main filler, that is, the amount of silica is markedly greaterthan the amount of any other fillers present.

When carbon black is present as the filler, preferably the amount ofcarbon black in the rubber mixture is from 1 to 150 phr, 2 to 100 phr, 2to 90 phr, 2 to 80 phr, 2 to 70 phr, 2 to 60 phr, 2 to 50 phr, 2 to 40phr, 2 to 30 phr, or from 2 to 20 phr. However, in some embodiments acarbon black is used that has an iodine adsorption number according toASTM D 1510 of 30 to 180 g/kg, 40 to 180 g/kg, or 40 to 130 g/kg, and aDBP number according to ASTM D 2414 of 80 to 200 ml/100 g, 90 to 200ml/100 g, or 90 to 150 ml/100 g.

The silicas contemplated herein include all silicas known to the personskilled in the art that are suitable as fillers for tire rubbermixtures. However, one embodiment includes a finely dispersed,precipitated silica having a nitrogen surface area (BET surface area)(according to DIN ISO 9277 and DIN 66132) of 35 to 350 m²/g, 35 to 260m²/g, 100 to 260 m²/g, or 130 to 235 m2/g and a CTAB surface area(according to ASTM D 3765) of 30 to 400 m²/g, 30 to 250 m²/g, 100 to 250m²/g, or 125 to 230 m²/g. Such silicas, when used, for example, inrubber mixtures for tire treads, produce particularly favorable physicalproperties of the vulcanizate. This also provides in some instancesadvantages in mixture processing by reducing mixing time while retainingthe same product properties, which leads to improved productivity. Inone embodiment, the silica incorporated into the described rubbermixtures includes the Ultrasil® VN3 type of silica (Evonik IndustriesAG, Essen, Germany) and highly-dispersible silicas such as theaforementioned HD silicas (for example, Zeosil® 1165 MP Rhodia-SolvayInternational Chemical Group, Brussels, Belgium).

To improve processability and to bind the silica and other polar fillersthat are in some embodiments present to the diene rubber, silanecoupling agents are used in various embodiments of the described rubbermixtures. In such embodiments, one or a plurality of different silanecoupling agents in combination with one another are used. The rubbermixture in some embodiments therefore contains a mixture of varioussilanes. The silane coupling agents react with the superficial silanolgroups of the silica or other polar groups during the mixing of therubber or of the rubber mixture (in situ), or even before adding thefiller to the rubber as a pretreatment (pre-modification). In suchembodiments, the silane coupling agents are any of those known to theperson skilled in the art as suitable for use in the disclosed rubbermixtures. Non-limiting examples of conventional coupling agents arebifunctional organosilanes possessing at least one alkoxy, cycloalkoxy,or phenoxy group on the silicon atom as a leaving group, and as theother functionality, having a group that can optionally undergo achemical reaction with the double bonds of the polymer after splitting.The latter group may, for example, constitute the following chemicalgroups: SCN, —SH, —NH2 or -Sx- (where x is from 2 to 8).

Contemplated silane coupling agents for use in such embodiments includefor example, 3-mercaptopropyltriethoxysilane,3-thiocyanato-propyl-trimethoxysilane, and3,3′-bis(triethoxysilylpropyl)-polysulfide with 2 to 8 sulfur atoms suchas, for example, 3,3′-bis(triethoxysilylpropyl)tetrasulfide (TESPT), thecorresponding disulfide (TESPD), and mixtures of the sulfides with 1 to8 sulfur atoms having a differing content of the various sulfides. Forexample, TESPT is also suitable to be added as a mixture with industrialcarbon black (X50S®, Evonik Industries AG, Essen, Germany).

In another embodiment, a silane mixture is used that contains up to 40to 100 wt % of disulfides, 55 to 85 wt % of disulfides, or 60 to 80 wt %of disulfides. This type of mixture, described by way of example in U.S.Pat. No. 8,252,863, is obtainable by way of example with Si 261® (EvonikIndustries AG, Essen, Germany). Blocked mercaptosilanes such as thoseknown from WO 99/09036 are also contemplated to be used as silanecoupling agents. Silanes such as those described in U.S. Pat. Nos.7,968,633; 7,968,634; 7,968,635; and, 7,968,636, as well as U.S. Pat.App. Pub. Numbers US 20080161486; US 20080161462; and US 20080161452 A1,or any combination thereof, are also in some embodiments incorporatedinto the disclosed rubber mixtures. Suitable are, for example, silanesmarketed under the name NXT in different variants by the firm Momentive,USA, or those marketed under the name VP Si 363® by the firm EvonikIndustries.

Moreover, in some embodiments, the rubber mixtures also contain carbonnanotubes (CNT), including discrete CNTs, so-called hollow carbon fibers(HCF), and modified CNT containing one or a plurality of functionalgroups such as hydroxy, carboxy, and carbonyl groups.

Graphite, graphene, and so-called “carbon-silica dual-phase fillers” arealso suitable as fillers.

Moreover, the rubber mixtures in some embodiments contain other polarfillers, such as, for example, aluminosilicates, chalk, starch,magnesium oxide, titanium dioxide, or rubber gels.

In one embodiment, the rubber mixture is free from other fillers, thatis, in this embodiment the rubber mixture comprises 0 phr of any otherfiller. In this embodiment, it is therefore not necessary to add anysecond filler.

For the purposes of the present disclosure, zinc oxide is not consideredto be a filler.

In one embodiment, the rubber mixture contains 0 to 70 phr, 0.1 to 60phr, or 0.1 to 50 phr of at least one plasticizer. These include one ormore of all plasticizers known to the person skilled in the art, such asaromatic, naphthenic, or paraffinic mineral oil plasticizers, forexample, MES (mild extraction solvate) or TDAE (treated distillatedaromatic extract), rubber-to-liquid (RTL) oils or biomass-to-liquid(BTL) oils, factices, plasticizing thermoplastic resins, or liquidpolymers (such as liquid BR), whose average molecular weight (determinedby gel permeation chromatography (GPC), based on BS ISO 11344:2004), isbetween 500 and 20,000 g/mol. If liquid polymers are used in the rubbermixtures described herein as plasticizers, these are not included asrubber in calculating the composition of the polymer matrix.

If a mineral oil is used, the mineral oil is selected from, for example,one or more of DAE (distillated aromatic extracts) and/or RAE (residualaromatic extracts) and/or TDAE (treated distillated aromatic extracts)and/or MES (mild extracted solvents) and/or naphthenic oils and/orparaffinic oils.

Moreover, the rubber mixtures disclosed herein contain in someembodiments various common additives in the commonly known number ofparts by weight. These additives include:

a) antioxidants such as, for example,N-phenyl-N′-(1,3-dimethylbutyl)-p-phenylene diamine (6PPD),N,N′-Diphenyl-p-phenylene diamine (DPPD), N,N′-ditolyl-p-phenylenediamine (DTPD), N-Isopropyl-N′-phenyl-p-phenylene diamine (IPPD),N,N′-Bis(1,4-dimethylpentyl)-p-phenylenediamine (77PD), and2,2,4-trimethyl-1,2-dihydroquinoline (TMQ),

b) activators such as, for example, zinc oxide and fatty acids (forexample, stearic acid),

c) waxes,

d) thermoplastic resins, in particular adhesive thermoplastic resins,

e) mastication auxiliaries such as, for example,2,2′-dibenzamidodiphenyldisulfide (DBD), and

f) processing auxiliaries, for example, fatty acid salts such as, forexample, zinc soaps, fatty acid esters and derivatives thereof.

In particular, in the use of the rubber mixtures disclosed herein forthe internal components of a tire or a technical rubber article that arein direct contact with the reinforcing supports present, a suitableadhesive system, often in the form of adhesive thermoplastic resins, isalso generally added to the rubber.

The proportion of further additives contained in the entire amount is 3to 150 phr, 3 to 100 phr, or 5 to 80 phr.

The proportion of further additives contained in the entire amount alsoincludes 0.1 to 10 phr, 0.2 to 8 phr, or 0.2 to 4 phr of zinc oxide(ZnO).

This zinc oxide useful in these embodiments includes of any type knownto the person skilled in the art, such as, for example, ZnO granulate orpowder. Generally speaking, conventionally used zinc oxide shows a BETsurface area of less than 10 m²/g. However, so-called nano zinc oxidehaving a BET surface area of 10 to 60 m²/g is also contemplated.

Vulcanization is performed in the presence of sulfur or sulfur donorsusing vulcanization accelerators, with some vulcanization acceleratorsalso being capable of acting as sulfur donors. Sulfur, or sulfur donors,and one or a plurality of accelerators, are added in the last mixingstep in the aforementioned amounts to the rubber mixture. Here, theaccelerator is one or more of thiazole accelerators and/or mercaptoaccelerators and/or sulfenamide accelerators and/or thiocarbamateaccelerators and/or thiuram accelerators and/or thiophosphateaccelerators and/or thiourea accelerators and/or xanthogenateaccelerators and/or guanidine accelerators.

Suitable accelerators include, for instance those selected fromN-cyclohexyl-2-benzothiazole sulfenamide (CBS) and/orN,N-dicyclohexylbenzothiazole-2-sulfenamide (DCBS),N-tert-butyl-2-benzothiazyl sulfenamide (TBBS), mercapto benzothiazole,tetramethyl thiuram disulfide, benzothiazole disulfide, diphenylguanidine, zinc dithiocarbamate, alkylphenol disulfide, zinc butylxanthate, N-dicyclohexyl-2-benzothiazolesulfenamide,N-cyclohexyl-2-benzothiazole sulfenamide, N-oxydiethylenebenzothiazole-2-sulfenamide, N,N-diphenyl thiourea, dithiocarbamylsulfenamide, N,N-diisopropylbenzothiozole-2-sulfenamide, zinc-2-mercaptotoluimidazole, dithio bis(N-methyl piperazine), dithiobis(N-beta-hydroxy ethyl piperazine), dithio bis(dibenzyl amine), andcombinations thereof. Other vulcanizing accelerators include, forexample, thiuram, and/or morpholine derivatives.

In one embodiment of the disclosed rubber mixtures, the mixturecomprises CBS as the accelerator. Particularly good tear properties arethus achieved for such rubber mixtures.

Further, network-forming systems such as for example those availableunder the brand names Vulkuren® (Lanxess, Shanghai, PRC), Duralink®(ChemLink, Schoolcraft, Mich., US), and Perkalink® (Lanxess, Shanghai,PRC), or network-forming systems such as those described in WO2010/059402, are also contemplated to be used in the rubber mixturesdescribed herein. This system contains a vulcanizing agent thatcrosslinks with a functionality greater than four and at least onevulcanization accelerator. The vulcanizing agent that crosslinks with afunctionality greater than four has, for example, General Formula A:G[C_(a)H_(2a)—CH₂—S_(b)Y]_(c)  A

where G is a polyvalent cyclic hydrocarbon group and/or a polyvalentheterohydrocarbon group and/or a polyvalent siloxane group that contains1 to 100 atoms; where each Y contains sulfur-containing functionalitiesindependently selected from a rubber-active group; and where a, b and care whole numbers for which the following applies independently: aequals 0 to 6; b equals 0 to 8; and c equals 3 to 5.

The rubber-active group is one or more of a thiosulfonate group, adithiocarbamate group, a thiocarbonyl group, a mercapto group, ahydrocarbon group, and a sodium thiosulfonate group (colored saltgroup). This allows achievement of highly favorable abrasion and tearproperties of the rubber mixture according to the invention.

Within the scope of the present disclosure, sulfur and sulfur donors,including sulfur-donating silanes such as TESPT, curing agents and curessuch as those described in EP 2288653, vulcanization accelerators asdescribed above, and vulcanizing agents that crosslink with afunctionality of greater than 4 as described in WO 2010/059402, such as,for example, a vulcanizing agent of Formula A), and the aforementionedsystems Vulkuren® (Lanxess, Shanghai, PRC), Duralink® (ChemLink,Schoolcraft, Mich., US), and Perkalink® (Lanxess, Shanghai, PRC), arecombined under the term vulcanizing agents.

The rubber mixture according to the disclosure includes, in someembodiments, at least one of these vulcanizing agents. This makes itpossible to produce vulcanizates, in particular for use in vehicletires, from the rubber mixture according to the disclosure.

In some embodiments, vulcanization retarders are present in the rubbermixture.

As known in the art, there is typically a “trade off” between rollingresistance and wet braking in tire technology. Often when one of thesetwo elements is improved, the other is worsened. Thus, an improvement inrolling resistance (RR) is often accompanied by a worsened performanceof wet braking, and vice versa. This is the RR-wet braking targetconflict. Embodiments encompassed by this disclosure therefore includetires that possess surprisingly improved rolling resistance with nochange in wet braking. Thus, an object of the disclosed rubbercompositions is to provide a vehicle tire that exhibits improved rollingresistance behavior, as well as snow performance. This object isachieved in that the vehicle tire contains the rubber mixtures accordingto this disclosure in at least one component as described above. In thiscontext, all of the aforementioned embodiments of the constituents andproperties thereof apply.

In one embodiment, the component is a tread. As known to the personskilled in the art, the tread contributes to a relatively high degree tooverall rolling resistance of the tire. In particular, high resistanceto cracking and crack propagation in the tread is also advantageous. Inone embodiment, the rubber compositions described herein are useful inother parts of the tire as well and can comprise various tire componentsand various tire component compounds. The tires can be built, shaped,molded and cured by various methods that are known and will be readilyapparent to those having skill in such art.

Another object of the present disclosure is improved snow performance.For instance, when the modified thermoplastic resins disclosed hereinare incorporated into a tire tread, such as Kristalex® F-85, themodified Kristalex® F-85 exhibits an improved RR-wet breaking targetconflict.

The modified Kristalex® F-85 thermoplastic resin, and indeed otherthermoplastic resins modified in this manner, possess a higher Tg value.One could then compare the performance of resins of similar Tg values toshow additional surprising performance features of the rubber mixturesincorporating one or more of the disclosed modified thermoplasticpolymers. For instance, one can compare the performance of the modifiedKristalex® F-85 thermoplastic resin to an un-modified Kristalex® F-115thermoplastic resin, since the unmodified Kristalex® F-115 thermoplasticresin possesses a similar Tg value as the modified Kristalex® F-85thermoplastic resin. In such an embodiment, it is surprisingly observedthat the unmodified Kristalex® F-115 exhibits surprisingly decreasedperformance, for instance especially in snow performance, as comparedwith the similar Tg value modified Kristalex® F-85 thermoplastic resin.Additionally, the wear or abrasion performance of tire treads, and otherrubber products, is substantially and surprisingly improved as comparedwith rubber products that do not incorporate the disclosed modifiedthermoplastic resins.

Further, as noted above, the modified Kristalex® F-85 thermoplasticresin tire exhibits superior performance in the RR-wet target conflict,as shown in the examples below. Thus, incorporation of the modifiedthermoplastic resins disclosed herein imparts surprising performanceimprovements in tires, such as pneumatic tires, for instance pneumatictires for use by an automobile, and the like.

A further object of the disclosure is to optimize the abrasion behaviorand the tear properties of technical rubber articles such as, forexample, belts, straps, brakes, and hoses without having a significantnegative effect on other properties that are relevant for the respectiveuse.

This object is achieved by using the above-described rubber mixtures forthe production of technical rubber articles such as, for example, belts(for instance, conveyor belts, automobile engine belts such as timingbelts, driving belts, and the like), straps, seals, tubes, and hoses.Another such technical rubber article is a shoe sole, for instance forwalking shoes, running shoes, cross-training shoes, boots, slippers,etc., items that are to be worn on the feet to protect the feet andassociated bones and joints from damage caused by jarring or poundingmotions associated with walking, running, jumping, etc. and to provideexcellent resistant to slipping in wet and/or dry conditions. Variousmethods are known in the art for incorporation of rubber mixtures intofootwear. See, for example, U.S. Pat. App. Pub. Nos.: 2013/0291409,2011/0252671, and U.S. Pat. No. 8,689,381 (all incorporated by referencein their entirety for all purposes).

The term body mixture as used here refers to rubber mixtures for theinternal components of a tire. Internal tire components essentiallyinclude the squeegee, side wall, inner liner (inner layer), coreprofile, belt, shoulder, belt profile, carcass ply, bead wire, cableprofile, horn profile, and bandage.

Manufacturing of these disclosed rubber mixtures is performed by themethods commonly used in the rubber industry, in which a basic mixturewith all of the constituents except the vulcanization system (sulfur andvulcanization-affecting substances) is first produced in one or aplurality of mixing stages. The finished mixture is produced by addingthe vulcanization system in a last mixing stage. The finished mixture isfurther processed, for example, by means of an extrusion process, andgiven the corresponding form.

For use in vehicle tires, the mixture is preferably made into a treadand applied in the known manner in production of the vehicle tire blank.However, the tread in some embodiments is also wound onto a tire blankin the form of a narrow rubber mixture strip. In two-part treadembodiments (upper part: cap and lower part: base), the rubber mixtureaccording to the disclosure is used both for the cap and for the base.

Manufacturing of the rubber mixture according to the disclosure for useas a body mixture in vehicle tires is performed as described above forthe tread. The difference lies in the molding after the extrusionprocess. The forms of the rubber mixture according to the disclosureobtained in this manner for one or a plurality of various body mixturesare then used to produce a tire blank. To use the rubber mixtureaccording to the disclosure in belts and straps, in particular inconveyor belts, the extruded mixture is made into the corresponding formand, at the same time or thereafter, often provided with reinforcingsupports, for example, synthetic fibers or steel cords. In most cases,one obtains a multilayer structure composed of one and/or a plurality oflayers of the rubber mixture, one and/or a plurality of layers of thesame and/or different reinforcing supports, and one and/or a pluralityof further layers of the same and/or another rubber mixture.

Unless otherwise defined, all technical and scientific terms used hereinhave the same meaning as commonly understood by one of ordinary skill inthe art. Although methods and materials similar or equivalent to thosedescribed herein can be used in the practice or testing of the presentinvention, suitable methods and materials are described below. Allpublications, patent applications, patents, and other referencesmentioned herein are incorporated by reference in their entirety for allpurposes. In case of conflict, the present specification, includingdefinitions, will control. In addition, the materials, methods, andexamples are illustrative only and not intended to be limiting.

EXAMPLES

A variety of modified thermoplastic resins have been prepared and testedin rubber mixtures for vehicle tires. These modified thermoplasticresins have also been prepared and tested in other compositions, such asadhesives and the like. The synthetic routes and the experimental dataare provided below.

The modified thermoplastic resins can be synthesized using the differentmethodologies provided hereinbelow, as well as other methodologiesapparent to one of skill in the art upon reading the methods providedbelow. All chemical reagents were from Sigma-Aldrich (St. Louis, Mo.,US), unless otherwise noted.

Example 1: Method of Modifying Thermoplastic Resin

A wiped film evaporation technique was selected for the separation ofthe oligomers from the thermoplastic resin. An 80% solution ofKristalex™ F-85 (Eastman Chemical Co., Kingsport, Tenn., US) in lightaromatic solvent naphtha was applied to a laboratory-scale wiped filmevaporator (Fischer Scientific, Hampton, N.H., US) to remove theoligomer fractions of the thermoplastic resins. The feed rate wasadjusted to a residence time of 20 seconds on the evaporator. Theevaporator temperature was set 280° C. and the pressure was 1.2 mBarA.At these conditions a modified Kristalex™ F-85 resin was made that had aTg of about 61° C., Table 4. In Table 5, the physical properties ofmodified thermoplastic resin made from C9, C5, C5/C9, hydrogenatedaromatic-modified DCPD, hydrogenated and partially hydrogenated C9, andhydrogenated PMR, and non-hydrogenated PMR resins that were producedusing the below described wiped film evaporator technique with processconditions for temperature ranging from 240 to 320° C. and for pressureranging from 0.01 to 1013 mBarA. The columns marked “T (° C.)” and “P(mBarA)” correspond to the conditions used during the modificationprocess.

FIG. 2 shows the result of the separation measured with high resolutiongel permeation chromatography. The separation was carried out on anAgilent OligoPore column (300×7.5 mm, Agilent Technologies, Santa Clara,Calif., US). The solid line is the starting material and the dashed linethe distilled product GPC analysis in FIG. 3.

Exemplary GPC traces of the starting thermoplastic resins Picco® AR85,Picco® A100, and Piccotac® 1095 (Eastman Chemical Company, Kingsport,Tenn., US), and modified thermoplastic resins of the same, are shown inFIG. 4.

An exemplary high resolution TGA trace showing weight loss versustemperature for a modified DCPD thermoplastic resin is shown in FIG. 5.An exemplary trace showing weight loss versus temperature for anunmodified PMR thermoplastic resin is shown in FIG. 6. An exemplarytrace showing weight loss versus temperature for a modified PMRthermoplastic resin is shown in FIG. 7.

This method was repeated for several different types of thermoplasticresins including those of the PMR, hydrogenated DCPD, C9, C5/C9, and C5type.

As noted, the molecular weight distribution was determined by GPCanalysis, and the glass transition temperature was determined using DSC.The softening point was determined using a Herzog model HRB 754 (PAC,L.P., Houston, Tex., US) and the ring and ball method (Standard TestMethods for Softening Point of Hydrocarbon Resins and Rosin Based Resinsby Automated Ring-and-Ball Apparatus, ASTM D6493-11(2015)). The valuesobtained for Mn, Mw, Mz, Mp, Tg, and SP are provided in Table 4, below.

TABLE 4 Comparison of Physical Parameters of Modified and Non-ModifiedThermoplastic Resins Mn Mw Mz Mp Tg [° C.] SP [° C.] Kristalex ® F-85650 1050 1700 880 40 86 Kristalex ® F100 790 1350 2150 1200 54 100Kristalex ® F-115 1015 1989 3500 1735 71 115 Modified 830 1200 1800 88062 105 Kristalex ® F-85

Further, the values of Mn, Mw, Mz, Tg, T₁₀, T_(max), and percentoligomer content as measured by high resolution TGA, as well as S valuedetermined using methodologies described hereinbelow. The values of thethermoplastic resins tested are presented in Table 5. (Picco®,Piccotac®, Regalite®, Regalrez®, and Kristalex® are from EastmanChemical Co., Kingsport, Tenn., US; Escorez® is from ExxonMobil ChemicalCompany, Spring, Tex., US). It is noted that when there is more entryfor a particular starting resin, such as for Piccotac™ 1095N, forexample, reading from left to right in Table 5, there are indicated twodifferent test conditions (temperature and pressure) for the samestarting resin. Furthermore, the Oligomer term is provided in Table 5 asa percentage, i.e. Oligomer×100, with respect to Formula I.

TABLE 5 Physical Parameters of Modified Thermoplastic Resins % StartingResin T P Mn Mw Mz Resin < % Resin < Resin type (° C.) (mBarA)(g/mol)^(¥) (g/mol)^(¥) (g/mol)^(¥) 600 g/mol^(¥) 300 g/mol^(¥)Kristalex ™ PMR 280 60 838 1092 1476 16 0.07 3085 Kristalex ™ PMR 2650.5 1046 1415 2115 ND ND F-85 Piccotac ™ C5 270 5 1028 1860 3947 13 11095N Piccotac ™ C5 270 0.05 1233 2051 4155 5 0.6 1095N Regalite ™ C9 H2280 0.5 650 928 1512 35 4 R1100 Regalite ™ C9 H2 320 0.05 699 975 150923 3 S7125 Regalite ™ C9 H2 280 0.25 682 1018 1663 28 3 S7125 Regalite ™C9 H2 300 3 587 851 1417 41 7 S7125 Regalite ™ C9 H2 280 1.2 574 8371521 42 7 S5100 Kristalex ™ PMR 320 0.5 1046 1407 2079 7 0.3 F-85Regalite ™ C9 H2 300 0.5 660 951 1536 33 5 R1100 Regalrez ™ PMR 240 1013566 757 1017 43 8 1094 H2 Regalrez ™ PMR 240 1013 669 1041 1660 30 81126 H2 Regalrez ™ PMR 240 400 722 1018 1510 27 3 1126 H2 Regalrez ™ PMR240 760 634 778 984 38 2 1094 H2 Picco ® C9 319 0.03 962 1308 2139 ND NDA100 Kristalex ® PMR 319 0.01 936 1048 1219 4 0.4 3070 Escorez ® H2 3180.03 660 843 1179 34 2 5600 DCPD Piccotac ® C5 318 0.01 1345 2231 4432ND ND 1095 Piccotac ® C5 318 0.01 1320 2181 4300 ND ND 1095 Escorez ® H2299 0.02 621 811 1174 39 4 5600 DCPD Picco ® C9 319 4.8 785 1133 1915 232 A100 Piccotac ® C5 269 0.01 1178 2047 4213 ND ND 1095 Kristalex ® PMR280 1.2 851 1268 2078 ND ND F-85 Escorez ® H2 299 0.5 540 740 1185 49 95600 DCPD Kristalex ® PMR 275 1.2 693 841 1061 ND ND 3070 Piccotac ®C5/C9 280 2 923 1587 3382 ND ND 7590-N Picco ® C9 280 2 696 1170 2523 NDND A100 Picco ® C9 280 2 629 787 1138 ND ND AR100 Piccotac ® C5/C9 280 21023 2158 5430 ND ND 8090-E Piccotac ™ C5 280 2 964 1823 4078 ND ND 1095Piccotac ™ C5 280 2 1365 3552 9529 ND ND 1105-E Picco ™ C9 280 2 644 8241171 ND ND AR85 Picco ™ C9 269 4.9 679 1070 2003 ND ND A100 S^(¥) S^(¥)Starting (<600 (<300 Tg T₁₀ T_(max) % Resin g/mol) g/mol) (° C.)¹ (°C.)² (° C.)² Oligomer² S² Kristalex ™ 56 965 63 336 350 3 361 3085Kristalex ™ ND ND 7 338 353 4 195 F-85 Piccotac ™ 17 166 57 335 366 10 16 1095N Piccotac ™ 229 2042 69 349 359 3 169 1095N Regalite ™ 17 135 91351 384 11  43 R1100 Regalite ™ 47 349 96 355 375 7 128 S7125 Regalite ™28 209 89 346 368 7 85 S7125 Regalite ™ 11 62 74 325 369 17  22 S7125Regalite ™ 10 63 69 331 371 14  26 S5100 Kristalex ™ 266 16567 76 348356 2 572 F-85 Regalite ™ 17 119 90 357 387 10  54 R1100 Regalrez ™ 23121 72 313 334 6 183 1094 Regalrez ™ 43 167 89 318 328 3 449 1126Regalrez ™ 83 671 84 327 334 3 829 1126 Regalrez ™ 50 983 71 328 340 3586 1094 Picco ® ND ND 103 353 355 1 3980 A100 Kristalex ® 1135 11478 66363 367 1 4051 3070 Escorez ® 85 1187 112 409 417 3 1012 5600 Piccotac ®ND ND 77 348 356 2 299 1095 Piccotac ® ND ND 75 347 356 3 217 1095Escorez ® 42 427 105 399 413 4 383 5600 Picco ® 33 384 83 343 358 5 166A100 Piccotac ® ND ND 68 343 354 3 138 1095 Kristalex ® ND ND 61 343 3605 113 F-85 Escorez ® 26 144 89 385 401 6 221 5600 Kristalex ® ND ND 44318 348 10  61 3070 Piccotac ® ND ND 57 330 349 6 52 7590-N Picco ® NDND 70 328 356 9 33 A100 Picco ® ND ND 66 307 349 16  27 AR100 Piccotac ®ND ND 50 333 353 7 25 8090-E Piccotac ™ ND ND 62 334 359 8 25 1095Piccotac ™ ND ND 6 350 369 6 20 1105-E Picco ™ ND ND 51 296 347 18  19AR85 Picco ™ ND ND 72 314 355 141  19 A100 ^(¥)Determined by GPC,¹determined by DSC, ²determined by high resolution TGA “ND” = no dataavailable

Likewise, similar physical parameters were analyzed for non-modifiedthermoplastic resins for comparison to the modified thermoplasticresins. The parameters of the non-modified thermoplastic resins arereflected in Table 6, below. (Plastolyn® is from Eastman Chemical Co.,Kingsport, Tenn., US; Oppera® is from ExxonMobil Chemical Company,Spring, Tex., US; Sylvares® and Sylvatraxx® are from AZ Chem Holdings,LP, Jacksonville, Fla., US; Sukorez® and Hickotack® are from KolonIndustries, Inc., South Korea; Wingtack® and Norsolene® are from CrayValley Hydrocarbon Specialty Chemicals, Exton, Pa., US).

It can be seen from the data in Tables 5 and 6 that the modificationprocess primarily reduces the value of Mn (number average molecularweight) due to the removal of the low molecular weight oligomer content,i.e. the dimer, trimer, tetramer, and/or pentamer molecules in thethermoplastic resin. The high molecular weight fraction of the modifiedthermoplastic resins, as indicated by Mz, is nearly unchanged ascompared to non-modified thermoplastic resins, i.e. the physicalparameters of the thermoplastic resins measured before modification. Byremoving the low molecular weight, low Tg fraction, the thermoplasticresin Tg increases significantly. This is also reflected in the increasein ring and ball softening point temperature.

These data also show that such modifications can be made to any numberof commercially available thermoplastic resins at least of the PMR, PMRH2, DCPD, DCPD H2, C5, C5 H2, C9, C9 H2, C5/C9 H2, and C5/C9 types.Values in Tables 5 and 6 are determined using the methodologiesdescribed further below.

TABLE 6 Physical Parameters of Representative Unmodified ThermoplasticResins Starting Resin Mn Mw Mz % Resin < % Resin < S^(¥) (<600 S^(¥)(<300 Tg T₁₀ T_(max) % Resin type (g/mol)^(¥) (g/mol)^(¥) (g/mol)^(¥)600 g/mol^(¥) 300 g/mol^(¥) g/mol) g/mol) (° C.)¹ (° C.)² (° C.)²Oligomer² S² Kristalex ® F-115 PMR 1030 2099 3945 15 3 14 67 67 316 3428 26 Kristalex ® F-115 PMR 1009 2145 4094 ND ND ND ND 67 299 334 12 12Kristalex ® F-85 PMR 680 1123 1930 31 7 4 18 39 284 361 22 6 Piccotac ®1115 C5 1132 3310 9977 13 3 8 39 60 346 366 8 14 Plastolyn ® R1140 C9 H2730 1437 2820 24 8 6 17 85 330 393 20 7 Plastolyn ® R1140 C9 H2 726 15613392 25 9 4 12 84 324 391 23 5 Plastolyn ® R1140 C9 H2 744 1601 3311 238 5 13 84 324 393 20 5 Regalite ® R1100 C9 H2 460 772 1427 50 19 3 7 48277 383 40 3 Regalite R1125 C9 H2 601 989 1616 34 11 5 17 72 315 393 296 Regalite ® S5100 C9 H2 522 894 1643 42 15 3 10 48 287 376 32 4Regalite ® S5100 C9 H2 562 933 1757 39 12 4 12 49 286 370 28 5Regalite ® S7125 C9 H2 625 1202 2453 32 11 4 15 71 315 379 22 6 Regalrez1094 PMR H2 510 710 959 46 13 8 26 41 284 335 18 23 Regalrez ® 1126 PMRH2 623 1016 1629 32 10 ND ND 62 ND ND ND ND Kristalex ® 3085 PMR 6901106 2359 28 6 9 42 42 312 344 11 23 Picco ® A120 C9 712 1588 3489 ND NDND ND 74 320 357 11 15 Kristalex ® 3070 PMR 590 771 1013 ND ND ND ND 30282 355 23 11 Escorez ® 5637 H2 DCPD 437 637 1052 60 19 5 17 80 359 43233 10 Hickotac ® P90S C9 635 1075 1937 ND ND ND ND 51 300 362 18 9Kristalex ® 3085 PMR 666 983 1451 ND ND ND ND 37 281 345 23 9 Picco ®AR100 C9 565 765 1124 ND ND ND ND 52 278 351 30 8 Fuijan SanmmingTerpene 659 1007 1680 ND ND ND ND 87 245 317 22 8 Sylvatraxx ® 4401 PMR659 1190 1935 ND ND ND ND 37 268 352 17 7 Escorez ® 5340 H2 DCPD 297 508903 73 39 4 7 86 333 441 37 7 Piccotac ® 7590-N C5/C9 743 1480 3350 NDND ND ND 41 299 356 17 6 Sylvares ® SA85 PMR 729 1359 2241 ND ND ND ND41 273 364 17 6 Kristalex ® F-85 PMR 661 1139 2044 ND ND ND ND 39 284359 25 5 Escorez ® 5600 H2 DCPD 386 592 890 ND ND ND ND 54 310 427 44 5Kristalex ® 3105 SD PMR 847 1271 2022 21 4 12 66 59 298 339 52 5 Picco ®A100 C9 528 1062 2413 ND ND ND ND 48 272 356 22 5 Kristalex ® F-100 PMR817 1547 2871 ND ND ND ND 54 282 347 24 4 Norsolene ® W100 PMR 768 12832184 ND ND ND ND 55 286 350 34 4 Regalite ® S5100 C9 H2 499 851 1648 NDND ND ND 46 274 371 33 4 Picco ® AR85 C9 482 683 989 ND ND ND ND 35 235353 42 4 Oppera ® PR373N C5/C9 716 1502 4289 ND ND ND ND 42 291 354 21 3Eastotac ® H-142R C5 H2 412 721 1621 ND ND ND ND 89 316 433 40 3Piccotac ® 8090-E C5/C9 783 1965 5286 ND ND ND ND 39 286 352 18 3Sukorez ® SU400 H2 DCPD 300 506 942 72 44 3 4 54 291 429 51 3 Piccotac ®1105-E C5 986 3324 9464 ND ND ND ND 46 311 364 15 3 Piccotac ® 1095 C5737 1694 4131 ND ND ND ND 42 285 368 21 3 Norsolene ® W85 PMR 619 10741805 ND ND ND ND 37 256 352 50 2 Eastotac ® H-130R C5 H2 372 702 1591 NDND ND ND 73 282 433 47 2 Wingtack ® 95 C5 1000 1727 3148 ND ND ND ND 51264 369 31 2 Eastotac ® H-100E C5 H2 308 743 2133 ND ND ND ND 43 237 42948 1 Eastotac ® H130W C5 H2 423 735 1648 58 23 2 5 75 443 57 43 3Escorez ® 5320 H2 DCPD 265 591 1801 74 41 1 2 64 301 442 39 2

Example 2: Analytical Characterization of Modified Resins, GeneralMethods

General methods: Differential scanning calorimetry (DSC) and highresolution thermogravimetric analysis (TGA) were used to evaluatethermal stability. GPC was used to determine any molecular weightchanges.

DSC was performed with a TA Instruments Q200 (TA Instruments, NewCastle, Del., US) under nitrogen at 20° C./min. Values from the secondheating scan were reported for heat, cool, heat cycles. High resolutionTGA was conducted under nitrogen with a TA Instruments Q500 (TAInstruments, New Castle, Del., US) at heating rate of 10° C./min.

A TA Instruments Q2000 Differential Scanning calorimeter (DSC) with anRCS 90 cooling system (TA Instruments, New Castle, Del., US) wascalibrated using the same heating rate, purge gas, and flow rate as wasused during sample analysis. Indium was weighed and prepared in astandard aluminum pan and was used to calibrate the temperature asoutlined in ASTM E 967.

Samples were prepared by weighing 3 to 5 mg of thermoplastic resin intostandard aluminum pans. Both the sample mass and pan mass were recordedand entered into the TA software for analysis. During sample testing,nitrogen was purged through the cell with a flow rate of 50 ml/min.Samples were cooled to zero degrees Celsius and held isothermal for twominutes before heating to 135° C. with a heating rate of 20° C./min.This heating cycle was repeated and the second heating scan was used foranalysis.

TA Instruments Universal Analysis software (TA Instruments, New Castle,Del., US) was employed for the analysis of samples. The second heatingscan of samples were analyzed for a step change or glass transition(Tg). The step midpoint was set at the half height between the onset andend of the Tg. Initial and final limits for the transition were manuallyselected where approximately 20° C. of steady baseline was observedbefore the onset and following the end of the Tg.

GPC methodologies were as follows: an Agilent 1100 HPLC (AgilentTechnologies, Inc., Santa Clara, Calif., US) equipped with refractiveindex detector (RID) was used for the GPC analysis. (See, for instance,Mulder et al., J. Chrom. A, 51:459-477, 1970). The sample was preparedby dissolving 25 mg of material in 10 mL of THF and sonicated for about5 min. Then, 10 μL of toluene was added and swirled. A portion of thissolution was added to a vial. Run Method: Flow: 1 mL/min, Solvent: THF,Runtime: 26 min, RID Temp: 30° C., Column Temp: 30° C., Injection: 50μL, Calibration Material: EasiCal PS-1 (Agilent Technologies, Inc.,Santa Clara, Calif., US, Part Number 2010-0505), Column Type: 1stColumn: GPC Guard Column (Agilent Technologies, Inc., Santa Clara,Calif., US, Part Number PL1110-1520), Particle Size—5 μm, Length: 50mm×7.5 mm, 1st Column: PLGel 5 μm MIXED-C, Part Number—PL1110-6500,Particle Size—5 μm, Length: 300 mm×7.5 mm, 2nd Column: OligoPore(Agilent Technologies, Inc., Santa Clara, Calif., US, Part NumberPL1113-6520), Particle Size—6 μm, Pore Type—100A, Length: 300 mm×7.5 mm.

An Agilent 1100 HPLC with an Agilent 1260 Refractive Index detector wasused for GPC analysis (Agilent Technologies, Inc., Santa Clara, Calif.,US). The mobile phase used was tetrahydrofuran stabilized with BHTpreservative (Mollickrodt Pharmaceuticals, Inc., Staines-upon-Thames,England, UK). The stationary phase consisted of three columns fromAgilent: PLgel MIXED guard column (5 micron, 7.5×300 mm, AgilentTechnologies, Inc., Santa Clara, Calif., US), PLgel Mixed C Column (5micron, 7.5×300 mm, Agilent Technologies, Inc., Santa Clara, Calif.,US), and an OligoPore GPC column (5 micron, 7.5×300 mm, AgilentTechnologies, Inc., Santa Clara, Calif., US).

The calibrants used were monodisperse polystyrene standards with amolecular weight (MW) range from 580 to 4,000,000 although peaks forpolystyrene dimer, trimer tetramer, and pentamer, were also observed andincluded in the calibration. Analytical grade toluene was used as flowmarker. A fourth-degree polynomial equation was used to find the bestfit for the Log MW versus the observed retention time. The instrumentparameters used for calibration and sample analysis include a flow rateof 1.0 ml/min, injection volume of 50 microliters while the columns andRI detector were heated at 30° C. Samples were prepared by dissolving 25mg of the sample into 10 ml of THF with BHT, after which 10 microlitersof toluene was added as the flow marker. Samples were analyzed todetermine the Mw, Mn, and Mz of the thermoplastic resins. The percentthermoplastic resin below 300 g/mol and below 600 g/mol, including theamount below 300 g/mol, was determined by GPC integration with AgilentGPC/SEC Software Version 1.2.3182.29519.

The instrument parameters used for calibration and sample analysisinclude a flow rate of 1.0 ml/min, injection volume of 50 microliterswhile the columns and RI detector were heated at 30° C. Samples wereprepared by dissolving 25 mg of the sample into 10 ml of THF with BHT,after which 10 microliters of toluene was added as the flow marker.Samples were analyzed to determine the Mw, Mn, and Mz of thethermoplastic resins.

In the high resolution TGA analyses of oligomer percentages (Tables 6and 7), a TA Instruments Q500 Thermal Gravimetric Analyzer wascalibrated using the curie point of magnetic transition standards asoutlined in ASTM method E1582, procedure C. It was calibrated with arate of 10 degrees per minute in Nitrogen using Alumel, Nickel,Perkalloy, Iron and room temperature. A small aluminum pan was paced ona platinum pan and tared before analysis. Between ten and twelvemilligrams of thermoplastic resin sample was placed inside the aluminumpan for analysis. The sample was heated in nitrogen with a scanning rateof 20 degrees per minute from ambient temperature to 625° C., using aresolution factor of 3.0 and Hi-Res sensitivity of 2.0.

Samples were analyzed by features observed in the weight percent versustemperature thermogram and the first derivative curve of the samevariables. The temperature at the maximum 1st derivative value, T_(max),is used as a reference temperature, and the percentage of oligomer isobtained by taking the percent weight loss at a temperature 30° C.below, T_(max). If the first derivative is multimodal and the T_(max) isreasonably assigned to oligomers, then the second maximum temperature inthe first derivative should be designated as T_(max). Additionally, thetemperature at 10% weight loss, T₁₀, is also determined.

The Verband Der Automobilindustrie E.V. (VDA) method 278 (VDA 278) testsfor volatile to medium volatile substances in the VOC value measurement,allowing substances to be determined and analyzed up to n-pentacosane(C25H52, 353 g/mol). (See, VDA 278 Thermal Desorption Analysis ofOrganic Emissions for the Characterization of Non-Metallic Materials forAutomobiles, for the Characterization of Non-Metallic Materials forAutomobiles, issued 29 Sep. 2011, updated October 2011, issued by theGerman Association of the Automotive Industry (VDA), Behrenstraße 35,10117 Berlin, Germany). This is the same carbon number cited in theEuropean Food Contact Material 95 definition for mineral oil. VDA 278also reports a FOG value that is the total of substances in the boilingpoint range of n-alkanes C₁₄H₃₀ to C₃₂H₆₆ 198-451 g/mol. Mineral oilshave been characterized by Vavasour and Chen of the World HealthOrganization as having a relative average molecular mass of 300 to 600g/mol. (See, Vavasour et al., WHO FOOD ADDITIVES SERIES: 50, “Safetyevaluation of certain food additives/prepared by the fifty-ninth meetingof the Joint FAO/WHO Expert Committee on Food Additives,” 2003, “MINERALOILS (MEDIUM-AND LOW-VISCOSITY) AND PARAFFIN WAXES”). Thus,characterization of the modified thermoplastic resins by the percent ofthe resin material that has a molecular weight below 600 g/mol and alsothe resin fraction that has a molecular weight below 300 g/mol (includedin the percentage under 600 g/mol) is characterized herein.

Standard molecular weight values were used for typical the resinmonomers including styrene, AMS, DCPD, DCP, indene, and piperylene.Modified thermoplastic PMR resins and C9 resins, including hydrogenated,partially hydrogenated, and comonomer-modified PMR and C9 resins,generally have trimer, tetramer, and pentamer oligomers possessing amolecular weight between about 300 g/mol and about 600 g/mol. The dimersof these resins possess a molecular weight of between about 100 g/moland about 300 g/mol. The other types of resins, such as C5, C5/C9, DCPD,aromatic-modified-DCPD, and other comonomer modified versions of theseresins, as well as hydrogenated and partially hydrogenated versions ofthese resins, comprise dimers and trimers that have molecular weightsgenerally between about 100 g/mol and about 300 g/mol, and tetramer andpentamer oligomers of a molecular weight of between about 300 g/mol andabout 600 g/mol. C5 resins and DCPD resins, and their correspondinghydrogenated and partially hydrogenated versions, without aromaticmodification, generally possess tetramer oligomers having a molecularweight of between about 100 g/mol and about 300 g/mol.

Example 3: Reduction of Volatile Organic Compounds (VOC) and FOG

Modified thermoplastic resins (C9 H2, PMR H2) were prepared and testedaccording to Verband Der Automobilindustrie E.V. (VDA) method 278.Unmodified commercial thermoplastic resins Regalite™ 55100, Regalite™R1100, Regalrez 1126, and Regalrez 1094 (Eastman Chemical Company,Kingsport, Tenn., US) were tested for comparison.

An Agilent 7890B gas chromatograph with an Agilent 5977A MS detector wasequipped with a Restek Rtx-5MS 30 meter (m)×0.25 millimeter (mm)×0.25 μmcolumn (Restek Corporation, Bellefonte, Pa., US) with 10 m deactivatedIntegra guard and connected to a PerkinElmer Turbomatrix ATD650(PerkinElmer, Waltham, Mass., US). A 15 to 20 mg sample was cut from theinterior of a pellet and inserted into a stainless-steel desorption tubeand held in place with glass wool. According to the VDA 278 method, thesample was heated in the thermal desorption tube for 30 minutes at 90°C. for volatile organic compound (VOC) gas emissions followed by 60minutes at 120° C. for condensable substance (FOG) emissions. For each,the emissions were collected on a Tenax cold trap (Tenax Corporation,Baltimore, Md., US) and then desorbed onto a GC column for separation,then sent into a mass selective detector (MSD) for identification andquantification.

The VOC value is the total of the readily volatile to medium volatilesubstances. This method allows substances to be determined and analyzedup to n-pentacosane (C25). The FOG value is the total of substances inthe boiling point range of n-alkanes C14 to C32. Quantitation isachieved by external calibration and is reported as toluene equivalentconcentrations for the VOCs and n-hexadecane equivalent concentrationsfor the FOGs. Sample values identified by * were tested by the sameprocedure on an Agilent 7890B gas chromatograph with an Agilent 5975A MSdetector was equipped with an Agilent DB-5MS 30 m×0.25 mm×0.25 μm columnwith 5 m deactivated fused silica guard column and connected to aGerstel Thermal Desorption System (TDS) using 30 mg samples (AgilentTechnologies, Santa Clara, Calif., US).

The results for VOC as toluene equivalents and the results for FOG asn-hexadecane equivalents in Table 7 show that the modified thermoplasticresins have a surprising 65% to 96% decrease in VOC and 80% to 97%decrease in FOG compared to currently commercially available unmodifiedresins. This makes the described modified thermoplastic resins withreduced VDA 278 VOC and FOG values uniquely advantageous forapplications involving use of adhesives, plastic modification, filmmodification, and thermoplastic elastomeric compounds where decreasingodor, air pollution, and/or migration of low molecular weight componentsare of interest. Such applications include, but are not limited to,window sealants for buildings, adhesives sealants, gaskets, seals,o-rings, molded parts, extruded parts, and such for automobiles, trucksand other motor vehicles, woodworking adhesives, carpet backingcompounds and adhesives, flooring adhesives, duct tape, mastics, andsealants, and the like.

TABLE 7 VDA 278 Performance of Modified and Unmodified ThermoplasticResins modified modified modified Regalite ™ modified Regalrez ™Regalrez ™ Regalrez ™ Regalrez ™ Regalrez ™ Regalrez ™ Resin tested 1126Regalrez 1126 S5100 S5100 R1100 R1100 1094 1094 Resin type PMR PMR C9 C9H2 C9 H2 C9 H2 PMR PMR H2 H2 H2 H2 H2 RBSP (° C.) 122  132  100 116 102140  94 121 VOC (μg/g 194*  68* 1400 270 1240 250  701*  26* as tolueneequivalents) FOG (μg/g 794* 155* 11250 1550 10650 270 3313*  93* as nC16^(Φ) equivalents) ^(Φ) nC16 = n-hexadecane *defined as above

Example 4: Compatibility of Binary Blends of Modified ThermoplasticResins

Two of the modified thermoplastic resins, specifically the modifiedRegalite™ R1100 thermoplastic resin and the modified Regalite™ S5100thermoplastic resin of Example 3, Table 7, modified Kristalex F-85 and asecond modified Regalite™ R1100 thermoplastic resin were prepared andcombined (50 wt %) with the specified metallocene-polyethylene (m-PE) orethylene vinyl acetate (EVA) polymers (50 wt %) in an aluminum trayheated on a hot plate to approximately 150° C. These blends were mixedwith a spatula until homogeneous or for a maximum of 10 minutes.Commercial resins Plastolyn™ R1140, Kristalex™ F-115, and Regalite™S5100 (Eastman Chemical Company, Kingsport, Tenn., US) were incorporatedinto comparative resin blends. Additionally, the same two modifiedRegalite™ R1100 thermoplastic resins were combined (20 wt %) with anextrusion grade polypropylene (PP) polymer with 3 g/min Melt Flow Rate(MFR), 230° C./2.16 kg (79.9 wt %) and 0.1 wt % Irganox® 1010(pentaerythritoltetrakis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate), BASF,Ludwigshafen, Germany) at 200° C. and 35 rpm for 10 minutes in aBrabender measuring mixer W50EHT (C.W. Brabender Instruments, Inc.Hackensack, N.J., US). Commercial resin Plastolyn™ R1140 was used tosimilarly prepare a comparative blend. The modified thermoplasticresins, specified polymers, and prepared blends were characterized byDSC, and the obtained values are provided in Tables 8A and 8B, below.

The Fox Equation (1/T_(g,mix)≈Σ_(i) ω_(i)/T_(g,i)) is well-known todescribe the Tg of a polymer blend when the components are fullycompatible with each other. The magnitude of deviation from thepredicted Fox Tg is sometimes considered an indication of compatibilitywith a fully compatible system having zero difference between thepredicted Fox Tg and the actual measured Tg of the prepared blend. Theblends provided herein including the described modified thermoplasticresins were as much as 5° C. closer to the predicted Fox Tg than thecomparative blends, indicating significantly improved compatibility ofthe modified thermoplastic resins in the polymers as compared withunmodified standard resins. It was especially surprising that thepolypropylene (PP) blends comprising inventive resins and PPE1 and PPE2had Tg values within 1° C. of the predicted Fox Tg values. Additionally,blends comprising the inventive modified resins were clear or had lesshaze than the comparative blends, indicating the improved compatibilityof the inventive resins in the polymers tested.

TABLE 8A Compatibility Of Modified Thermoplastic Resins With PolymersPolypropylene (PP) AFFINITY ™ GA1950 (3 g/10 min MFR, 230° C./2.16 kg)Modified Modified Modified Modified Polymer Regalite ™ Regalite ™Plastolyn ™ Regalite ™ Regalite ™ Plastolyn ™ test resin R1100 R1100R1100 R1100 R1140 R1100 Polymer (%) 50 50 50 80 80 80 Resin (%) 50 50 5020 20 20 DSC Tg, resin 93.9 92.7 90.2 93.9 92.5 84.9 DSC Tg, −51.5 −51.5−51.5 −2.0 −2.0 −2.0 polymer DSC Tg, −31.5 −31.5 −36.8 22.9 22.0 17.8Blend-actual DSC Tg, 3.2 2.9 2.2 21.9 21.9 20.2 blend-Fox predictedDifference 34.7 34.4 39.0 −0.9 −0.1 2.3 (Fox predicted Tg-actual blendTg) ° C. improved 4.3 4.6 reference 1.4 2.2 reference compatibility MeltClear at Clear at Haze = 4 at Clear at Clear at Haze = 1 at appearance160° C. 160° C. 160° C. 215° C. 215° C. 215° C. (5 = opaque)

TABLE 8B Compatibility Of Modified Thermoplastic Resins With PolymersEvatane ™ 40-55 Evatane ™ 28-150 Modified Polymer Modified Kristalex ™Regalite ™ Regalite ™ test resin Kristalex ™ F-85 F-115 S5100 S5100Polymer (%) 50 50 50 50 Resin (%) 50 50 50 50 DSC Tg, resin 76.7 67.670.1 50.0 DSC Tg, polymer −24.6 −24.6 −28.8 −28.8 DSC Tg, −5.1 −11.9−7.1 −17.2 Blend - actual DSC Tg, blend - Fox 17.5 14.3 12.3 5.1predicted Difference (Fox 22.6 26.2 19.4 22.3 predicted Tg - actualblend Tg) ° C. improved 3.6 — 2.9 — compatibility Melt appearance Haze =2, 160° C. Haze = 5, 160° C. Haze = 1, 160° C. Haze = 1, 160° C. (5 =opaque, 1 = clear)

Example 5: HMPSA Compositions Containing Modified Thermoplastic C5Resins

Modified thermoplastic resins (C5) were prepared and combined in theratios shown below in Table 9 to create Hot Melt Pressure SensitiveAdhesives (HMPSAs) TE1, TE2, and TE3 (all values are in phr). Anonmodified thermoplastic resin (C5), Piccotac™ 1115 (Eastman ChemicalCompany, Kingsport, Tenn., US), was used to prepare comparative adhesiveTC1. The styrene block copolymer adhesives were mixed in a 1 Kg capacityLinden sigma-blade mixer attached to a Julabo Hot Oil TemperatureControl Unit (Julabo Labortech GmbH, Seelbach, Germany). The mixer waspre-heated for 45 minutes using oil at 170° C., resulting in a typicalmixer temperature of approximately 150° C. The styrene block copolymer,antioxidant, and half the resin were charged under nitrogen and mixedfor approximately 12 minutes or until homogenous. Each subsequentcomponent addition was mixed for 5 to 10 minutes before another additionwas made. Thermoplastic resin was added in thirds, followed by additionof about one-third the specified oil, and the remaining oil was added inthree portions. The final composition was mixed for an additional 30minutes, with a typical final adhesive temperature of 150° C.

TABLE 9 HMPSA Formulations for PSA Tape Testing Containing Modified C5Resins TC2 TE1 TE2 TE3 Kraton ™ D1160 100 100 100 100 Piccotac ™ 1115115 0 0 0 Modified Piccotac ™ 0 115 0 0 1095N Modified Piccotac ™ 0 0115 100 1095N Nyflex ® 820 oil 15 15 15 15 Antioxidant Irganox ® 0.010.01 0.01 0.01 1010

Viscoelastic characteristics of Comparative Adhesive TC2 and ExampleInventive Adhesives TE1, TE2, and TE3 were characterized by DynamicMechanical Analysis (DMA), and the values obtained are provided in Table10. The viscosity of the prepared adhesives was measured following ASTMD-3236, Brookfield Engineering Laboratories Model DV-II, spindle 29.Relative finger tack within a set of samples was independently evaluatedby three operators and the average values are reported in Table 10.

The modified thermoplastic resin adhesives exhibit increased Tan-δ peakvalue corresponding to excellent compatibility of the modifiedthermoplastic resins with the polymer midblock, resulting in increasedadhesive tack as compared to the unmodified resin-containing comparativeexample.

TABLE 10 Comparison of Physical Parameters of HMPSA formulated withModified and Non-Modified Thermoplastic Resins TC2 TE1 TE2 TE3   ResinRBSP (° C.) 113 107 117 117 Properties of the HMPSA HMPSA RBSP (° C.)134 133 134 148 Brookfield viscosity 109,800 120,700 152,000 188,000  at 180° C. (cP) Finger tack +/− +++ ++ +++ DMA Tan-δ peak 9.2 7.2 13.27.2   temperature (° C.) DMA Tan-6 peak value 1.5 1.9 1.9 1.8 DMA 3rdcross over 123 125 128 127 temperature   (Tan-δ = 1) (° C.)

The prepared HMPSA formulations were coated onto 2 mil Mylar (BoPET,biaxially-oriented polyethylene terephthalate) film using a Bobis hotmelt knife coater at 180° C. (LC200 lab-coater produced by Maan Group,Raalte, The Netherlands). The comparative HMPSA formulation was coatedat 190° C. to obtain good flow. Tapes were tested after 24 hours at 23°C./50% RH and after aging two weeks in an oven at 40° C. Tapeperformance tests were conducted according to AFERA 5001 (180° peelstrength, stainless steel, n=4), AFERA 5012 (static shear adhesion, n=4,23° C./2.5 kg, 40° C./1 kg and 70° C./0.5 kg), AFERA 5013 GTF 6001(Shear Adhesion Failure Temperature, SAFT, n=4, 0.5 kg), and FTM-9 (looptack, n=4). The results of these tests are presented in Table 11.

The coat weights were 18±1 g/m², and coated tape samples wereconditioned in a controlled temperature and humidity climate (25° C. and50% RH) overnight before testing as pressure sensitive adhesive tapes.

Loop tack tests were performed on a Instron tensile tester type 3344with 50 N load cell in accordance with PSTC-16 Instron Corporation,Norwood, Mass., US). The crosshead displacement rate was 5 mm/s. A 25mm×125 mm loop of tape was used in the experiments. The free loop oftape, unrestricted by the grips, was 75 mm long. The contact area of theloop was 25 mm×25 mm, and the maximum force per unit width of thespecimen was recorded. The initial height, measured from the bottom ofthe grips to the substrate surface, was 50 mm. The maximum displacementwas 44 mm and the dwell time at maximum displacement was one second.

Shear Adhesion Failure Temperature (SAFT) measurement followed AFERA5013 GTF 6001 Test Method for Shear Adhesion Failure Temperature (SAFT)of Pressure Sensitive Tape and was measured using a Shear Test Ovenequipped with a High Temperature Shear Bank Tester (ChemInstruments,Fairfield, Ohio, US). A 25×25 mm (1″×1″) area of tape was adhered to astainless-steel panel using one complete pass of a standard 2 kg (4.5lb.) hand roller. Samples were prepared and climatized for 30 minutes at25° C. and 50% RH, then placed in the oven and a static load of 500 gwas suspended from the tape. The oven was equilibrated for 20 minutes at40° C., and then the temperature was increased with a heating rate of0.5° C./minute. The measured time to failure was recorded and convertedto a failure temperature in degrees Celsius (° C.). The minimum numberof samples for SAFT testing was four.

Shear holding power measurements were performed with a modification ofthe AFERA 5012 method, Self Adhesive Tapes—Measurement of Static ShearAdhesion EN 1943 2002, using a shear tester. These experiments wereconducted to measure the room temperature, cohesive, or shear propertiesof the adhesive tape. A 25 mm×25 mm (1″ by 1″) contact area described inAFERA 5012 was used. The pressure-sensitive adhesive tape (PSAT) wasadhered to stainless steel coupons with a standard 4.5 lb. (2 kg) rollerand a mass of 2.5 kg was suspended from the tape. The time (h) at whichthe adhesive failed cohesively was recorded as the holding power. Afterreaching a maximum time of 167 h (10,000 min), the samples were removedfrom the test apparatus. Samples for shear holding power at 70° C. weresimilarly prepared. Samples were placed in an oven and were climatizedto 70° C. After reaching this temperature, the static load of 500 g wassuspended from the tape. The measured time to failure was recorded. Theminimum number of samples tested was four.

The 180° peel resistance or peel force per unit width was measured inaccordance with AFERA 5001: Self Adhesive Tapes—Measurement of PeelAdhesion from Stainless Steel or from its own Backing—Single-CoatedTapes, Peel Adhesion at 180° Angle. Rectangular strips of tape measuring25 mm×250 mm were tested using an Instron Model 3344 at 5 mm/s (12inch/minute) crosshead displacement rate (Instron, Norwood, Mass., US).Results were recorded in N/25 mm.

The excellent compatibility of the modified thermoplastic resins in theadhesive yielded superior tack with over 100% improvement in loop tack,and superior adhesion with over 50% higher peel strength. Surprisingly,the modified thermoplastic resin provided superior performance in tack,adhesion, and cohesion with superior cohesive strength as indicated bylonger shear adhesion at 23° C. after aging, and improved temperatureresistance as indicated by higher SAFT temperatures of TE2 and TE3.Surprisingly, the inventive adhesives have superior cohesive strength athigh temperature, as indicated by more than 80% longer shear adhesion at70° C. Most surprising was that the 70° C. shear adhesion of TE3 wasover 400% longer than the 70° shear adhesion of TC1.

Furthermore, adhesive TE3 uses less resin to achieve higher temperatureresistance, cohesive strength, and tack as comparative adhesive TC2containing only unmodified resin. This means that the modifiedthermoplastic resin in TE3 is more effective per gram used in achievingthe desired tape performance properties than current commerciallyavailable unmodified thermoplastic resins.

TABLE 11 Performance of HMPSA Tapes Formulated with Modified andNon-Modified Thermoplastic Resins Test TC2 TE1 TE2 TE3 Loop tack tosteel 1.2 4.1 2.2 3.4 (N)-nitial Loop tack no tack 1.7 0.5 1.5 (N)-gedPeel adhesion 12.3 19.0 19.9 19.3 (N/25 mm)-nitial Peel adhesion 0.216.9 16.5 16.0 (N/25 mm)-aged Shear adhesion at >2 weeks >2 weeks >2weeks >2 weeks 23° C./2.5 kg (min)-initial Shear adhesion at no tack >2weeks >2 weeks >2 weeks 23° C./2.5 kg (min)-aged Shear adhesion at 42927781 8913 >2 weeks 70° C./0.5 kg (min)-initial Shear adhesion at notack >2 weeks 7183 >2 weeks 70° C./0.5 kg (min)-aged SAFT (° C.)- 112117 112 120 initial (σ = 1) SAFT (° C.)- No tack 113 117 120 aged

Example 6: Metallocene-Polyethylene Packaging Adhesive Compositions

Modified thermoplastic resin (C9 H2) was prepared and combined in theratios shown in Table 12 to prepare hot melt adhesive PE4. Thecomponents were placed in an aluminum tray heated on a hot plate toapproximately 150° C. The mixture was mixed with a spatula untilhomogeneous or for a maximum of 10 minutes. Non-modified thermoplasticresins (C9 H2) Regalite™ R1125 and Plastolyn™ R1140 (Eastman ChemicalCompany, Kingsport, Tenn., US) were used to similarly preparecomparative adhesives PC2 and PC4, respectively.

TABLE 12 Packaging Adhesive Compositions Containing Modified Resins PC2PC4 PE4 Resin RBSP (° C.) 125 139 140 AFFINITYGA ™ 1950 42 42 42 (wt %)Regalite ™ R1125 38 0 0 (wt %) Plastolyn ™ R1140 0 38 0 (wt %) ModifiedRegalite ™ R1100 0 0 38 (wt %) Wax (Sasol H1) 20 20 20 (wt %)Antioxidant 0.38 0.38 0.38 (Irganox ® 1010) (wt %)

The Brookfield viscosity was determined according to ASTM D3236,“Standard Test Method for Apparent Viscosity of Hot Melt Adhesives andCoating Materials” using a Brookfield Engineering Laboratories ModelDV-II equipped with a Brookfield Thermosel™ at the specified temperature(AMETEK Brookfield, Middleborough, Mass., US).

Visual appearance was determined manually with a rating of 1 (clear) to5 (opaque).

Bonded samples were prepared using either Substrate 1: corrugatedcardboard, flute type B, 220 g/m² Kraft liner, 220 g/m² Kraft liner,sourced from Rengo Co., Ltd., Japan, or Substrate 2: corrugatedcardboard, flute type B, 115 g/m² Kraft liner, 150 g/m² Test liner,sourced from Moorman (Royal Moorman Karton Weesp BV, Weesp,Netherlands).

Bonded samples for adhesion (fiber tear) testing and for open and settime measurement were prepared using an Adhesive Testing Unitmanufactured by ITW Dynatec GmbH, Mettmann, Germany, according toJapanese Adhesive Industry (JAI) Association Method JAI-7-B, withcardboard flutes perpendicular. The fiber tear test consists of manuallytearing glued cardboard substrates under the conditions of roomtemperature or 0° C. (low temperature fiber tear, LTFT). The gluedcardboard substrates were conditioned at temperature for at least 10hours before testing. Samples for SAFT and PAFT testing were preparedfollowing JAI Method JAI-7-A, and samples for hold power testing (peelmode) were prepared following JAI Method JAI-7-C. All samples wereprepared with a two second open time and a 20 second compression timewith 250 N contact pressure. A minimum of 8 specimens are tested foreach test. PAFT and SAFT testing was conducted with 100 g and 500 gweights, respectively and an oven ramp rate of 0.5° C./min. Hold powersamples were tested at the specified temperature using a 250 g weight.Set time determination used a 2 second open time and a contact pressureof 8 N. The set time was determined using the maximum pull force incombination with a minimum of 70% fiber tear.

The properties and performance of the prepared adhesives are presentedin Table 13. Surprisingly, the modified thermoplastic resin-containingadhesive PE4, prepared using modified 140° C. RBSP thermoplastic resin,is transparent at 160° C., while the adhesive prepared with standard140° C. resin PC4 has an unacceptable, almost opaque appearance. Thisindicates much greater compatibility of the modified 140° C. RBSPthermoplastic resin with the m-PE polymer, as shown in Example 4 andwith the overall adhesive formulation compared to the standard 140° C.RBSP resin. When the adhesive performance is compared to the transparentPC2 adhesive comprising the lower softening point, standard 125° C. RBSPresin, PE4 unexpectedly has comparable viscosity, and provides bothimproved heat resistance (PAFT) and improved −15° C. low temperaturefiber tear performance.

TABLE 13 Properties And Performance Of Metallocene-PolyethylenePackaging Adhesive Compositions Formulated With Modified AndNon-Modified Thermoplastic Resins PC2 PC4 PE4 RBSP of resin (° C.) 125139 140 Adhesive RBSP (° C.) 109 111 109 Brookfield Viscosity at 160° C.(cP) 2130 2295 2285 Visual appearance at 160° C. 1 5-opaque 1 (5 =opaque, 1 = clear) Visual appearance at 180° C. 1-clear 4-hazy 1 (5 =opaque, 1 = clear) PAFT-Substrate 2 (° C.) 81 87 87 Hold power, peelmode at 50° C.- >24 >24 >24 Substrate 1 (hr) SAFT-Substrate 2 (° C.) 8485 84 LTFT-15° C. Substrate 2 (%) 25 38 40 Set time-Substrate 1 (sec) 54 10

Example 7: Ethylene Vinyl Acetate Adhesive Compositions ContainingModified Resins

Modified thermoplastic resins were prepared and combined in the ratiosshown in Table 14 to prepare hot melt adhesives VVE5 (PMR) and VVE2 (C9H2). Non-modified thermoplastic resins (PMR) Kristalex™ F-85 andKristalex™ F-115 were used to prepare comparative adhesives VVC5 andVVC6, and Regalite™ S5090 and Regalite™ S5100 (C9 H2) were used toprepare comparative adhesives VVC1 and VVC2 (Eastman Chemical Company,Kingsport, Tenn., US). The adhesives are useful for packaging,woodworking and other similar applications. The adhesives were preparedand tested following standard methods as described in Example 7.

TABLE 14 EVA Adhesive Formulations Comprising Modified ThermoplasticResin VVC1 VVE2 VVC2 VVC5 VVE5 VVC6 Evatane ™ 28-150 40 40 40 0 0 0 (wt%) Evatane ™ 40-55 0 0 0 40 40 40 (wt %) Regalite ™ S5090 35 0 0 0 0 0(TK757) (wt %) Modified Regalite ™ 0 35 0 0 0 0 S5100 (wt %) Regalite ™S5100 0 0 35 0 0 0 (wt %) Kristalex ™ F-85 0 0 0 15 0 0 (wt %) ModifiedKristalex ™ 0 0 0 0 15 0 F-85 (wt %) Kristalex ™ F-115 0 0 0 0 0 15 (wt%) Regalite ™ R1100 0 0 0 20 20 20 (wt %) Wax (Sasol H1) (wt %) 15 15 1515 15 15 Paraffin wax 66-69 10 10 10 10 10 10 (wt %) Antioxidant(Irganox ® 0.4 0.4 0.4 0.4 0.4 0.4 1010) (wt %)

Surprisingly, inventive adhesive VVE2 was transparent using the higherRBSP modified thermoplastic resin, resulting in advantageously andsignificantly higher PAFT than VVC1 and 400% and 189% longer 50° C.holding power (peel) than VVC1 and VVC2, respectively, while maintainingadhesion at −15° C., Table 15. The high vinyl acetate content EVAadhesive VVE5 surprisingly was transparent with 100% improved 50° C.holding power (peel) compared to both VVC5 and VVC6, while maintainingadhesion at −15° C.

TABLE 15 Properties And Performance Of EVA Adhesive FormulationsComprising Modified Thermoplastic Resins VVC1 VVE2 VVC2 VVC5 VVE5 VVC6Resin RBSP 91 116 99 86 117 116 (° C.) Adhesive 107 109 108 108 107 107RBSP (° C.) Brookfield 2230 2790 2450 6500 7600 7200 Viscosity at 160°C. (cP) Visual 1 1 1 1 1 1 appearance at 160° C. (5 = opaque, 1 = clear)PAFT- 58 ± 1  68 ± 1  65 ± 1  85 ± 1.7  81 ± 1.1  82 ± 1.5 Substrate 1(° C.) HP at 50° C.- 13 ± 4  66 ± 25 23 ± 3  86 ± 42  171 ± 46  128 ±44  Substrate 1 (hr) LTFT −15° 43 ± 26 61 ± 34 75 ± 26 88 ± 27   88 ±21  98 ± 8  C. Substrate 1 (%) LTFT 0° C. 88 ± 28 95 ± 10 95 ± 15 90 ±17   93 ± 12   85 ± 21  Substrate 1 (%)

Example 8: Ethylene Vinyl Acetate Adhesive Compositions ContainingModified Resins

Modified thermoplastic resin (PMR) was prepared and combined in theratios shown in Table 16 to prepare two different hot melt adhesives,VE3 and VE7. An unmodified thermoplastic resin (PMR), Kristalex™ 3085,was used to prepare comparative adhesives VC1 and VC5 (Eastman ChemicalCompany, Kingsport, Tenn., US). Adhesive formulations were prepared bythoroughly mixing the specified polymers, resin, and antioxidant using amechanical stirrer equipped with a coil impeller, followed by additionof the specified waxes. The formulations were mixed for 15 minutes afterall additions were complete. Formulations VC1 and VE3 were mixed atabout 150° C. and applied at 130° C. to a cardboard substrate fortesting. Formulations VC5 and VE7 were mixed at about 180° C. andapplied at 180° C. to a cardboard substrate for testing.

TABLE 16 EVA Adhesive Formulations Comprising Modified ThermoplasticResin VC1 VE3 VC5 VE7 Evatane ™ 28-800 (wt %) 35 35 0 0  Evatane ™ 28-40(wt %) 0 0 38 38 Evatane ™ 28-420 (wt %) 0 0 42 42  Permalyn ™ 6110 (wt%) 5 5 0 0  Kristalex ™ 3085 (wt %) 30 0 80 0 VE7 Modified Kristalex ™ 030 0 80 3085 resin (wt %) Paraffin wax mp 29.6 29.6 0 0 66-69° C. (wt %)Sasolwax ™ 3279 0 0 40 40 microcrystalline     wax (wt %) Irganox ® 10100.4 0.4 0.6 0.6 antioxidant (wt %)

The Brookfield viscosity was analyzed according to ASTM D3236, “StandardTest Method for Apparent Viscosity of Hot Melt Adhesives and CoatingMaterials” using a Brookfield DV-I+ with Thermosel™ and spindle 27 atthe specified temperature (AMETEK Brookfield, Middleborough, Mass., US).

Bonded samples for fiber testing and for open and set time measurementwere prepared using hot melt tester model ASM-15N manufactured byMitsubishi Electric Corporation (MEC) in Japan according to MethodJAI-7-B, with cardboard flutes perpendicular. The fiber tear testconsists of manually tearing glued cardboard substrates by hand underthe conditions of room temperature or 0° C. The glued cardboardsubstrates were conditioned at temperature for at least 10 hours beforetesting. Samples for SAFT and PAFT testing were prepared followingMethod JAI-7-A, and samples for hold power testing (peel mode) wereprepared following Method JAI-7-C. PAFT and SAFT testing was conductedwith 100 g and 500 g weights, respectively at an oven ramp rate of 0.5°C./min. A minimum of 5 specimens are tested for each test. Hold powersamples were tested with a 250 g weight. All tests were conducted onSubstrate 1.

The properties and performance of the prepared adhesives are given inTable 17. The modified thermoplastic resins incorporated into adhesivesVE3 and VE7 exhibited a RBSP about 20° C. higher than the adhesivesformulated with unmodified resins. Surprisingly, despite thesignificantly higher resin RBSP, adhesives VE3 and VE7 incorporating themodified thermoplastic resins exhibit RBSP values and viscosity valuescomparable to those of control samples VC1 and VC5, respectively.

Although the higher RBSP modified thermoplastic resin analyzed by thisexample did not increase the adhesive viscosity, there was a surprisingand advantageous 400% increase in the 50° C. hold power of adhesive VE3comprising modified thermoplastic resin as compared to VC1 comprisingunmodified resin. VE3 and VE7 both exhibited improvement in set time,open time, and thermal resistance (PAFT). Additionally, adhesive VE7comprising modified thermoplastic resin surprisingly had significantlyimproved adhesion to cardboard at −7° C. as compared to adhesivescomprising standard unmodified resin. The modified thermoplastic resinstherefore allowed the use of higher RBSP resins without significantlyincreasing the RBSP and viscosity of the final adhesive, therebymaintaining the ease of processing and ability to use lower adhesiveapplication temperatures. Additionally, excellent performance wasobserved in terms of temperature resistance and setting properties whenincorporating the modified thermoplastic resins described herein intothese adhesive formulations.

TABLE 17 Properties Of EVA Adhesives Comprising Modified ThermoplasticResins VC1 VE3 VC5 VE7 Adhesive RBSP (° C.) 76 75 85 87 Viscosity 120°C. (cP) 1530 1709 7825 9525 Viscosity 140° C. (cP) 810 892 4215 4892Viscosity 160° C. (cP) 467 510 2400 2796 open time (sec) 8 4 30 27   settime (sec) 6 4 10 8 PAFT (JAI) (° C.) 55 ± 3  61 ± 2  47 ± 2  51 ± 2SAFT (JAI) (° C.) 69 ± 3  69 ± 2  62 ± 3  69 ± 3 hold power 50° C.  12 ±1.4 52 ± 17   8 ± 0.7 11 ± 2 (JAI peel) (min) Fiber tear (%) RT 100 100100 100  −7° C. 100 100 20 90 −15° C. 80 30 10 10

Example 9: SBS Nonwoven Construction Adhesive Compositions ContainingModified Resins

Modified thermoplastic resins (C9 H2) were prepared and combined in theratios shown in Table 18 to construct hot melt adhesives HE3, HE4, andHE5. An unmodified thermoplastic resin (C9 H2), Regalite™ S7125, wasused to prepare comparative adhesive HC3 (Eastman Chemical Company,Kingsport, Tenn., US). The procedures employed here were the same as inExample 5.

TABLE 18 Styrene-Butadiene-Styrene Block Copolymer (SBS) NonwovenConstruction Adhesives Comprising Modified Thermoplastic Resins HE3 HE4HE5 HC3 Resin RBSP (° C.) 141 135 121 121 SBS Europrene SolT 20 20 20 20 6414 (wt %) Modified Regalite ™ 60 0 0 0 S7125 (wt %) ModifiedRegalite ™ 0 60 0 0 S7125 (wt %) Modified Regalite ™ 0 0 60 0 S7125 (wt%) Regalite ™ S7125 (wt %) 0 0 0 60 Primol 352 Mineral oil 20 20 20 20(wt %) Irganox ® 1010 0.2 0.2 0.2 0.2 Antioxidant (wt %)

The properties of the adhesives prepared in this experiment are providedin Table 19. Modified thermoplastic resin-containing adhesive HE5 has alower RBSP and lower viscosity than comparative adhesive HC3 preparedwith standard unmodified resin, providing for easier processing andapplication of adhesive HE5. Additionally, adhesives HE3, HE4, and HE5show surprisingly excellent compatibility of the modified thermoplasticresins in the adhesives by the value of the Tan-δ peak being equal to,or greater than, the value of the Tan-δ peak of comparative adhesiveHC3, even when adhesive HE3 comprising modified thermoplastic resin isbased on a resin with an RBSP value that is significantly higher thanthe comparative resin.

TABLE 19 Properties of SBS Nonwoven Construction Adhesives ComprisingModified Thermoplastic Resins HE3 HE4 HE5 HC3 Resin RBSP (° C.) 141 135121 121 Properties of the HMA HMA RB SP (° C.) 104 100 95 100 Haziness 11 1 1 (5 = opaque, 1 = clear) Brookfield melt viscosity at 11750 103505760 7763 140° C. (Pa · s) Brookfield melt viscosity at 3725 3413 21502638 160° C. (Pa · s) Brookfield melt viscosity at 1610 1450 1010 1225180° C. (Pa · s) DMA Tan-δ peak temperature 37 35 25 29 (° C.) DMA Tan-δpeak value 4.2 3.2 4.9 3.5 DMA 3rd cross over temp (° C.) 99 95 89 94DMA G′ at 37° C. (10⁵ Pa) 1.6 2.0 4.6 6.0

Inventive adhesives HE4 and HE5 and comparative adhesive HC3 were coatedon 50 μm (2 mil) Mylar film using an in-house laboratory hot melt knifecoater at 150° C. The coat weights of 26±2 g/m², and coated tape sampleswere conditioned in a controlled temperature and humidity climate (25°C. and 50% RH) overnight before testing as pressure sensitive adhesivetapes. The results presented in Table 20 were unexpected. HE5 had 170%greater loop tack and more than 950% greater 180° peel adhesion onstainless steel than the comparative adhesive, HC3. Typically, anincrease in adhesion is accompanied by a decrease in cohesion, butsurprisingly HE5 and HE4 also had almost 950% and 200% longer hold(shear) power at 70° C., respectively. The increase in cohesion wasadditionally surprising since the SAFT temperatures were only slightlyincreased above the comparative adhesive HC3.

Test methods employed in this Example were as described previously forSAFT and PSA hold power, above. Loop tack followed PSTC-16 methodologyusing an MTS Criterion Universal Tensile Tester model C43-104E (MTSSystems Corporation, Eden Prairie, Minn., US). 180° peel adhesionfollowed the equivalent method PSTC 101: “Peel Adhesion of PressureSensitive Tape Test Method A—Single-Coated Tapes, Peel Adhesion at 180°Angle” using an MTS Criterion Universal Tensile Tester model C43-104E(MTS Systems Corporation, Eden Prairie, Minn., US). Rectangular stripsof 25 mm×250 mm (1″×10″) dimensions were tested at 5 mm/s (12inch/minute) crosshead displacement rate.

TABLE 20 Performance Of SBS Pressure Sensitive Adhesives ComprisingModified Thermoplastic Resins And Comparative Examples HC3 HE5 HE4 ResinRBSP (° C.) 121 121 135 HMA RBSP (° C.) 100 95 100 Performance of HMPSASAFT (1″ × 1″, 1000 g) 85 87 89 (σ = 3) (° C.) Loop tack on SS, avg.load, 2 6 0.1 (σ = 1) (lbf) 180° peel on SS, (σ = 0.3) (lbf/in) 0.7 7.50.1 70° C. Hold (1″ × 1″, 1000 g) 59 115 109 (σ = 21) (min)

Example 10: Non-Vulcanized Thermoplastic Elastomer Binary SEBS BlendsContaining Modified Thermoplastic Resins

Non-vulcanized thermoplastic elastomer test formulations were preparedby thoroughly mixing prepared modified thermoplastic resins (PMR, C9 H2)(20 wt %) and Kraton™ G-1650 styrene-ethylene/butylene-styrene blockcopolymer, Kraton Performance Polymers, (80 wt %) (Kraton Corporation,Houston, Tex., US). Formulation GE1 was prepared using modifiedKristalex® 3085 resin. Formulations GE2, GE3, and GE4 were preparedusing modified Regalite® S7125 resins. GE5 was prepared using modifiedRegalrez® 1094 resin. GE6 and GE8 were prepared using modified Regalrez®1126 resins. For comparison, unmodified thermoplastic resins (PMR, C9H2, PMR H2) Kristalex™ F-115, Regalite™ S7125, Regalrez™ 1094, Regalrez™1126, and Plastolyn™ R1140 (Eastman Chemical Company, Kingsport, Tenn.,US) were used to similarly prepare comparative formulations GC1, GC2,GC3, GC4, and GC5, respectively. A reference without resin was alsoprepared by processing neat polymer under the same time and temperatureconditions, GC0. Tables 21 and 22 provide the formulation test results,showing the surprising increase in tear strength, % modulus, andtensile, combined with the desirable decrease in compression set forbinary blends comprising modified thermoplastic resins.

The following test methods were utilized in this and the followingexperiments. Binary formulations were prepared by mixing in a BrabenderPL-2000 equipped with a Prep-Mixer™mixing bowl and roller blades (C.W.Brabender® Instruments, Inc., S. Hackensack, N.J., US) at 220° C. for 15minutes at 75 rpm. All of the blends were formed into plaques (5″×5″×⅛″)and (4″×4″×¼″) by compression molding in a heated Carver press at 180°C. and approximately eight tons of pressure for five minutes. Theplaques were tested for percent transmittance with a Gardner Haze-GardPlus No. 4725 instrument (BYK Additives and Instruments, Wesel,Germany). The films were then die cut into test articles for variousphysical tests including tear strength, tensile, and compression set.Remaining material was cut up into pellet sized pieces for melt flowrate measurements.

Tensile samples were die-cut and tested in accordance to ASTM D638 (TypeV) and tested on a MTS Criterion Universal Tensile Tester model C43-104E(MTS Systems Corporation, Eden Prairie, Minn., US). Tear samples weredie cut to compliance with ASTM D624 (die C).

Tensile strength, modulus and elongation at break were measured as perASTM D412 using a MTS Criterion Universal Tensile Tester model C43-104Eat a crosshead speed of 500 mm/min (MTS Systems Corporation, EdenPrairie, Minn., US). Tear strength was measured at the same conditionsfollowing ASTM D624. The results of six tests were averaged.

Melt flow rate was measured in a Ceast melt flow modular instrument at230° C. with a 2 kg weight (Instron, Norwood, Mass., US). Standarddeviation was typically 0.1.

For compression set testing, ASTM D395-14 was used. Test specimens wereconditioned to ambient lab temperature and humidity for 24 hours andthen cut from 6 mm thick plaques using a punch style cutter with aninner diameter of 13 mm. Three samples of each plaque were loaded into aplate compression device with 4.5 mm spacer bars for constant deflectionin accordance to test method B. Samples were then allowed to remainunder constant ambient lab conditions or in a 70° C. oven for 22 hours.Thickness measurements were taken before compression and 30 minutesafter a lab conditioning phase after being removed from the device. Thecalculated results are reported in accordance to ASTM 395-14; standarddeviation was typically 1%.

Hardness testing was conducted according to ASTM D2240-05. Samples weremeasured from the same 6 mm plaques used for compression testing, butonly before compression samples were cut. A “type B” Shore A durometerwas used along with a very dense lab bench as a base for testing.Measurements were collected and recorded in compliance with ASTMD2240-05.

Binary blend GE1 exhibited a desirable lower Shore A hardness thancontrol sample GC1, but surprisingly GE1 also exhibited a highlydesirable 9% decrease in compression set combined with a 26% increase intensile strength and 9% increase in elongation percent. Binary TPEblends GE2, GE3, and GE4 each exhibited as much as a 10% decrease incompression set compared to control sample GC2, while maintaining tearand tensile properties.

TABLE 21 Properties Of Non-Vulcanized Thermoplastic Elastomer BinarySEBS Formulation Containing Modified Thermoplastic Resins GC1 GC2 GE1GE2 GE3 GE4 GC0 Test resin RBSP (°) 115 121 107 121 135 141 n/aHardness-Shore A 83 81 80 79 81 80 68 Hardness-Shore D 24 22 24 21 22 2115 MFR 230° C./2.16 kg 2.3 1.4 2.0 1.3 0.9 1.2 <1 (g/10 min) Compressionset at RT 32 56 29 50 55 50 42 (%) Compression set at 92 87 93 87 890 8484 70° C. (%) % T 91 87 92 87 88 86 88 Tear Strength (lbf/in, 400 211305 207 220 205 142 ±20)  50% Modulus (psi, 821 385 750 374 405 374 259±20) 100% Modulus (psi, 814 367 773 360 397 348 311 ±20) 200% Modulus(psi, 872 362 840 374 402 357 338 ±20) 300% Modulus (psi, 975 376 938404 416 382 364 ±20) Tensile Strength (psi ± 2002 2400 2524 2142 25742248 615 300) Elongation (% ± 260) 2921 4020 3196 4041 3705 3967 2195

Formulations GE5, GE6, and GE8 comprising modified thermoplastic resinsall exhibited desirable decreased compression set as compared withcomparative examples comprising unmodified thermoplastic resins.Surprisingly, modified thermoplastic resins with RBSP as high as 140° C.lower the blend Shore A hardness, improve melt flow, percenttransmission, compression set, tear strength, tensile strength, andpercent elongation compared to controls comprising analogous standardunmodified resins, as shown in Table 22.

TABLE 22 Properties Of Non-Vulcanized Thermoplastic Elastomer BinarySEBS Formulations Comprising (Hydrogenated/PartiallyHydrogenated/Aliphatic) Modified Thermoplastic Resins GC0 GC3 GC4 GC5GE5 GE6 G E8 Resin RBSP no resin 94 122 140 112 132 138 (° C.)Hardness-Shore A 68 65 64 69 63 65 64 Hardness-Shore D 15 16 15 17 16 1615 MFR <1 2.1 1.8 1.0 1.7 1.5 1.1 230° C./2.16 kg (g/10 min) Compression41.7 22.7 23.4 31.6 21.2 22.2 26.1 set at RT (%) Compression 83.9 ± 1.585.2 ± 3.0 82.6 ± 1.5 79.7 ± 1.4 80.9 ± 1.3 81.4 ± 0.7 78.0 ± 0.3 set at70° C. (%) % T 88.3 89.5 91.3 90.3 90.9 91.2 89.8 Tear Strength 142 202199 257 206 223 218 (lbf/in, ±20)  50% Modulus 259 178 198 227 110 201156 (psi, ±20%) 100% Modulus 311 242 279 294 191 277 249 (psi, ±20) 200%Modulus 338 283 331 326 245 320 285 (psi, ±20) 300% Modulus 364 316 371358 278 354 312 (psi, ±20) Tensile 615 1734 1912 2756 2187 2243 2187Strength (psi ± 300) Elongation 2195 4053 4006 4015 4236 4224 3787 (% ±260)

Example 11: Non-Vulcanized TPE Binary SEBS Blend with Reduced Migration

Rectangular (4″×0.5″) pieces of GE6 and GC4 (samples from Example 10)were placed on a stainless-steel coupon, and a 6-inch diameter 4 kgbrass weight was placed on top of the samples. The assembly was placedin a 135° C. oven for 30 minutes. The brass weight was removed whilehot, and the surface was visually examined by two operators for evidenceof component migration from the TPE binary blend to the brass surface.Comparative sample GC4 left a residue image on the brass weight covering75 percent of an area twice the actual sample size, or about 150 percentof the sample area (Surprisingly, sample GE6 had a residue imagecovering only about 20 percent of the sample size, which is about 86%less area with residue than the comparative TPE binary blend. Table 23shows that the percent of original sample area that has visible residueon the brass surface is correlated with the VDA 278 VOC and FOG values,particularly the FOG values. This indicates that VDA 278 is a goodpredictor for not only the reduced VOC and FOG performance of adhesivecompositions comprising the modified thermoplastic resins with reducedoligomer content, but also for the ability of these modified resins toyield compositions with similar remarkable properties as are observed inthe resins themselves.

TABLE 23 Area With Visible Residue: Migration From Thermally Aged Non-Vulcanized Thermoplastic Elastomer Binary SEBS Blend ContainingHydrogenated/Aliphatic Modified Thermoplastic Resin GC4 GE6 modifiedRegalrez ™ Regalrez ™ 1126 1126 resin RBSP (° C.) 122 132 Residue after135° C. aging, percent 150  20 of original sample area (%) Resin VOC,VDA 278  194*   68* (μg/g as toluene equivalents) Resin FOG, VDA 278 794*  155* (μg/g as nC16 equivalents) *defined as above

Example 12: Non-Vulcanized Thermoplastic Elastomer Binary SEEPSFormulation Containing Modified Thermoplastic Resins

Modified thermoplastic resin (C9 hydrogenated) was prepared and combinedat 177° C. with Kuraray Septon™ 4033 in the ratio 20 wt % resin and 80wt % polymer to prepare TPE binary blends SE9 and SE10. Analogousunmodified thermoplastic resin Plastolyn™ R1140 was used to similarlyprepare comparative blend SC6. These blends were prepared and tested asdescribed in the previous example.

Compound SE9 comprising modified thermoplastic resin favorably decreasedthe compound Shore A, Shore D, and percent modulus. Unexpectedly, SE9both decreased compression set below SC0 and SC6 and increased tearstrength above the values of SC0 and SC6, as shown in Table 24.

TABLE 24 Properties of Non-Vulcanized Thermoplastic Elastomer BinarySEEPS Formulation Containing Modified Thermoplastic Resins SC6Plastolyn ™ SE9 Modified SC0 R1140 Regalite ™ R1100 Resin RBSP (° C.)n/a 140 140 Tear Strength (lbf/in, ± 20) 182 215 250  50% Modulus, (psi,± 20) 387 356 225 100% Modulus, (psi, ± 20) 377 347 282 200% Modulus,(psi, ± 20) 373 355 300 300% Modulus, (psi, ± 20) 397 384 321  TensileStrength (psi ± 300) 3438 3546 3190 Elongation (% ± 260) 4095 3971 3782Young's Modulus (ksi) 2.0 2.0 0.9 Hardness-Shore A 76 75 70Hardness-Shore D 20 20 18 % T 91 90 91 MFR-230° C./2.16 kg 0.5 1.5 1.8(g/10 min) Compression set at −RT (%) 34 31 24 Compression set at −70°C. (%) 86 82 81

Example 13: Removable SEBS Formulation with Reduced Residue IncludingVDA 278 VOC and FOG

Modified thermoplastic resin (PMR, hydrogenated) was prepared andcombined in the ratios set forth in Table 25 to prepare hot meltformulation RE1 and an analogous unmodified thermoplastic resinRegalrez™ 1094 (PMR hydrogenated) was used to prepare comparativeformulation RC1 (Eastman Chemical Company, Kingsport, Tenn., US). Blendswere mixed in a Brabender small bowl with roller blades at 150° C., asdescribed above. The blends were coated on 50 μm (2 mil) Mylar filmswith a hot melt knife coater at 160° C. at coat weights of 22-24 g/m².These coated tapes were then applied to stainless-steel coupons at roomtemperature, and 180° peel adhesion was tested after 10 minutes, asdescribed above following method PSTC 101. The compositions coated onMylar were tested per VDA 278 for VOC and FOG performance.

Both blends exhibited equivalent 180° peel strength. However,surprisingly, the blend comprising modified thermoplastic resin left noresidue on the stainless-steel (SS) coupon to which it had been applied,despite comprising mineral oil. This removable formulation isunexpectedly suitable for use in applications such as the adhesivelayers for protective films employed in a broad range of surfaces aswell as end uses aimed at protecting objects from mechanical (scratches)or chemical (e.g. from solvents) damage during transport, storage, andprocessing. Surprisingly, the improved VDA 278 performance of themodified thermoplastic resin resulted in significant anddisproportionate improvement in performance of composition RE1. Althoughthe composition is only 50 wt % thermoplastic resin, the RE1 compositioncomprising the modified thermoplastic resin had 82% reduction in VDA 278VOC value and 68% reduction in FOG value, compared to the compositioncomprising the unmodified resin. This result was surprising since thecomposition contained 11.5 wt % oil and additionally the composition wasnot crosslinked to reduce volatiles.

TABLE 25 Hot Melt Formulations Comprising Modified ThermoplasticHydrogenated PMR Resins Example RC1 RE1 Test resin Regalrez ™ Modified1094 Regalrez ™ 1094 Kraton ™ G1652 (phr)  50  50 Kraton ™ G1726 (phr) 50  50 Resin (phr)  130   0 Resin (phr)   0  130 Kaydol oil (phr)  30 30 Formulation performance 180° peel on SS (lbf/in) 0.13 ± 0.06 0.10 ±0.02 SS appearance in application Visible residue No residue area Blendon Mylar VDA 278  4285*  778* VOC (μg/g as toluene equivalents) Blend onMylar VDA 278  7700*  2453* FOG (μg/g as nC16 equivalents) *defined asabove

Example 14: Polypropylene Film Compounds Containing Modified Resins

Modified thermoplastic resin (C9 H2) was prepared and compounded (10 wt%) with Moplen HP400H polypropylene homopolymer (10 wt %)(LyondellBassell Industries, N.V., Rotterdam, The Netherlands). Allpolypropylene-resin compounding, cast film extrusion, and heat sealtesting were conducted at Fraunhofer Institute IVV in Freising, Germany,as described below.

Films were extruded using the main extruder of a Collin Teach-LineE30Px30L/D, Dr. Collin, Ebersberg, Germany, equipped with a single screwwith L/D 30, 30 mm screw diameter. The die width was 300 mm, resultingin a maximum final film width of 250 mm. A cooling/heating,chill-roll/calendar item with an edge trim and a winder were attached tothe extrusion components. Extruder temperature profile in ° C. was 30(feeding zone)-170-220-240-250-260 (zone 1 to 5)-260 (adapter and die)and screw speed 50 rpm. Winding speed was 3.7-3.9 m/min, and nominalfilm thickness was 70 microns as determined online by means of acapacitive sensor.

Heat-sealability of the films was determined using a Heat SealingMachine model HSG-C manufactured by Brugger Feinmechanik GmbH, Munich,Germany. The sealing conditions were 0.5 sec contact time, 5 barpressure, both jaws heated, non-profiled, smooth sealing jaws. Sealingseam strength was measured according to DIN 55529, 10 repeats, using aSchenck-Trebel RM50 testing machine (Schenck-Trebel Corporation, DeerPark, N.Y., US).

Water vapor transmission rate (WVTR) was measured in accordance withASTM F1249 at 38° C./90% RH using a Mocon PERMATRAN™-W 3/31 (MOCON Inc.,Minneapolis, Minn., USA). Reported values were corrected to 70 μmthickness.

The coefficients of friction were measured at 23° C., 50% RH using asled, in accordance with ASTM D1894, sled tested, on an MTS Insight™ 2EL electromechanical testing system, using TestWorks™ 4 testing software(MTS Systems Corporation, Eden Prairie, Minn., US). Tensile propertieswere measured at 2 in/min following ASTM D882 on an MTS Insight™ 2 ELwith gauge length 2 inches and 6″×0.5″ sample size. Haze andtransmission were measured on a Gardner Haze-Gard Plus instrument (BYKAdditives and Instruments, Wesel, Germany) according to ASTM D1003,method A.

The formulations compounded with thermoplastic resin had significantlylower melt pressure than the neat polymer, with an additional pressurereduction observed for the modified thermoplastic resin. This agreeswith the MFR of FFE1 surprisingly 6% higher than the MFR of FFC2, andthe with standard resin. The lower die pressure and higher melt flowrate give improved melt processing, reduces energy needed to orient afilm, and typically reduces line breaks and re-work.

As shown in Table 26, the modified thermoplastic resin also surprisinglyreduced the haze of the FFE1 film by about 30% compared to FFC2 film,and about 77% compared to the unmodified FFC1 film.

The static coefficient of friction between the FFE1 film and an ASTMD1894 sled was about 4% lower than the static COF for FFC2 film.Surprisingly, the water vapor transmission rate (WVTR) of the FFE1 filmwas about 18% lower than the control film FFC2 with standard resin,making use of this inventive resin advantageous to prevent providemoisture barrier properties combined with improved flow properties.

The sealing strength of a film is also an important parameter. TheMaximum force is the force needed to initiate the separation of thelayers or the tearing of the film, and the Mean force is the forceneeded to separate the sealing. FFE1 unexpectedly had greater than 50%higher maximum sealing force and mean sealing force. If the content ofinventive modified thermoplastic resins in the film is increased, thenthe sealing force of the compounded film will be increased, and likelythe strength of lamination to another substrate or film. Unexpectedly,it was noted that films with 20 phr and 30 phr modified thermoplasticresin have noticeable tack when handled, allowing cold lamination ofmultiple layers or application of films without use of an adhesivecoating. One skilled in the art would use such a higher modified resincontent compound alone or with one or more additional polymercompositions to form functional barrier films, protective films and thelike with improved performance.

TABLE 26 Properties of Polypropylene Film Compounds Comprising ModifiedThermoplastic Resins FFC1 FFC2 FFE1 Test Resin none Plastolyn ™ modifiedR1140 Regalite ™ R1100 Resin RBSP (° C.) n/a 138 140 Processing castfilm Thickness (mm) 0.07 0.07 0.07 Melt temperature (° C.) 263 263 264Melt pressure (bar) 147 115 111 Application results of cast film Initialsealing 143 137 <140 temperature (° C.) Max sealing temperature 147 143143 (shrinkage) (° C.) Seal strength at 143° C.- 4 ± 2 13 ± 4  18 ± 3 maximum force (N/15 mm) Seal strength at 143° C.- 2.6 ± 0.9 9 ± 2 14 ±4  mean force (N/15 mm) MFR 230° C./2.16 kg (g/10 min) 1.77 ± 0.07 2.52± 0.01 2.68 ± 0.08 Transparency (%) 94.2 ± 0.5  93.9 ± 0.1  94.3 ± 0.1 Haze (%) 7.5 ± 0.9 2.4 ± 0.2 1.7 ± 0.4 WVTR at 38° C./90% RH 3.63 ± 0.044.24 ± 0.19 3.45 ± 0.14 (g/(m²/day)) COF (23° C., 50% RH), sled- 0.32 ±0.05 0.397 ± 0.009 0.38 ± 0.03 static COF (23° C., 50% RH), sled- 0.27 ±0.01 0.31 ± 0.02 0.316 ± 0.008 dynamic Tensile strength, TD (MPa) 17 ±1  26 ± 1  24 ± 1  Tensile strength, MD (MPa) 22 ± 2  28 ± 1  28 ± 1 Elongation, TD (%) 4.2 ± 0.1 2.6 ± 0.4 2.3 ± 0.3 Elongation, MD (%) 7.8± 0.3 3.8 ± 0.1 3.6 ± 0.2 Tensile at break, TD (MPa) 40 ± 6  27 ± 4  24± 1  Tensile at break, MD (MPa) 61 ± 12 49 ± 8  55 ± 7  Elongation atbreak, TD (%) 831 ± 87  400 ± 364 2.4 ± 0.3 Elongation at break, MD (%)796 ± 112 749 ± 78  799 ± 35  Young's modulus, TD (MPa) 833 ± 62  1482 ±154  1365 ± 58  Young's modulus, MD (MPa) 963 ± 53  1284 ± 74  1283 ±73 

Example 15: Reduction of Mineral Oil Saturated Hydrocarbons (MOSH) andMineral Oil Aromatic Hydrocarbons (MOAH) Fractions in ModifiedThermoplastic Resins

Modified thermoplastic resins (C9 H2) were prepared and tested for thecontent of low molecular hydrocarbons (≤C35) employing methodologiesaccording to Grob et al. (Grob et al., J of Chromatography A, 1255:56,2012). Unmodified commercial thermoplastic resins Regalite™ 55090,Regalite™ 55100, and Regalite™ R1100 (Eastman Chemical Company,Kingsport, Tenn., US) were also tested for comparison.

A Brechbuehler AG LC-GC-FID system (Thermo Fisher Scientific, Waltham,Mass., US) was equipped with an Allure Silica column, Normal Phase, 5μm, 250 m×2.1 mm (Restek Corporation, Bellefonte, Pa., US). The flowrate was 0.3 ml/min with a backflush rate of 0.5 ml/min. Internalstandard solution was prepared in toluene and consisted of 300 mg/L eachof: n-undecane, cyclohexylcyclohexane, pentylbenzene,1-methylnaphthalene, 2-methyl-naphthalene, tri-tert-butyl-benzene, 150mg/L n-tridecane, and 600 mg/L each of cholestane and perylene. Standardcomponents were supplied by Restek. All solvents used for analysis wereanalytical grade supplied by Merck & Co., Kenilworth, N.J., US. Thesample extract was prepared by dissolving 30 mg sample in 20 mLn-hexane, and then 40 microliters of internal standard solution wereadded. Approximately 10 μl to 90 μl of the sample extract was injectedinto the HPLC. The gradient solvent program was as follows: Eluent A(n-hexane)—100% 0.0-0.5 min, 60% 0.6-6 min, 100% 15-30 min, and Eluent B(dichloromethane)—40% 0.6-6 min, 100% 6-15 min. The normal phase LC wasused for the separation of saturated (MOSH fraction) and aromatichydrocarbons (MOAH fraction). Polar components remained on theHPLC-column and were eluted into the waste during the backflush of thecolumn. No interference with MOSH and MOAH occurred. The fraction ofinterest was transferred (online) into GC-FID. The gas chromatograph wasequipped with a Restek Rxi-1HT 15 m×0.25 mm ID column (RestekCorporation, Bellefonte, Pa., US) and a 7 m×0.53 mm ID uncoatedprecolumn (Supelco Brand, Sigma-Aldrich, St. Louis, Mo., US).

Mineral oil saturated hydrocarbons (MOSH) and mineral oil aromatichydrocarbons (MOAH) are food contaminants that originate from printinginks that can enter the recycling chain through newspaper or printedboxes. MOSH/MOAH can migrate via gas phase into dry food (≤C24) ormigrate via wetting contact into fatty food (≤C35). MOSH in the range ofC16 to C35 can accumulate in human tissue and cause harmful healtheffects. The presence of MOAH is a potential concern as this isassociated with carcinogenic and mutagenic properties. (European FoodSafety Authority, Scientific Opinion on Mineral Oil Hydrocarbons inFood, EFSA Journal, 10(6):2704, 2012). Oligomers from thermoplasticresins can appear to be MOSH/MOAH contaminants and result in falsepositives in MOSH/MOAH testing, and reduction of the apparent MOSH/MOAHfractions is therefore desirable in certain end uses and relatedembodiments.

The results in Table 27 show that the modified thermoplastic resinsexhibit a surprising 94 to 98% decrease in the C16-C20 MOSH fraction, an86 to 96% decrease in the C20-C24 MOSH fraction, a 4 to 65% decrease inC24-C35 MOSH fraction, up to a 96% decrease in ≤C24 MOAN fraction, and a9 to 75% decrease in C24-C35 MOAN fraction, as compared with analogouscurrently commercially available unmodified resins. This makes thedescribed modified thermoplastic resins with reduced MOSH/MOAH fractionsuniquely advantageous for compositions and articles comprising thedescribed modified resins that are in contact with, or in closeproximity to, humans or animals and food products, as well as otherapplications similar applications.

TABLE 27 MOSH MOAH Performance of Modified and Unmodified ThermoplasticResins modified modified modified modified Regalite ™ Regalite ™Regalite ™ Regalite ™ Regalite ™ Regalite ™ Resin tested R1100 R1100R1100 S5100 S5090 S5100 Resin type C9 H2 C9 H2 C9 H2 C9 H2 C9 H2 C9 H2Resin RBSP (° C.) 102 140 138 100 116 120 MOSH Fraction: 45.3 1.8 2.834.2 0.4 1.9 C16-C20 (g/kg) MOSH Fraction: 11.2 0.9 0.6 8.3 0.3 1.1C20-C24 (g/kg) MOSH Fraction: 166.6 58.4 65.3 99.0 41 94.5 C24-C35(g/kg) MOAH Fraction: ≤0.2 ≤0.2 ≤0.2 5.6 ≤0.2 ≤0.2 ≤C24 (g/kg) MOAHFraction: 5.7 1.8 1.4 59.1 53.8 44.4 C24-C35 (g/kg)

Example 16: Rubber Composition Containing Modified Resins

A modified thermoplastic resin (PMR) was prepared and added to a rubbermixture in amounts of 20 phr and 40 phr to prepare rubber mixtures E1and E2, respectively, as shown in Table 28, below. Additionalnon-modified thermoplastic resin samples were prepared and added to arubber mixture in amounts of 0 phr, 20 phr, and 40 phr to prepare rubbermixtures W1, W2, and W3, and W4, W5, and W6, W7 respectively, as alsoshown in Table 27, below, where “6PPD” means antioxidantN-phenyl-N′-(1,3-dimethylbutyl)-p-phenylene diamine, “TESPD” means thedisulfide of silane coupling agent3,3′-bis(triethoxysilylpropyl)tetrasulfide, “DPG” means the accelerantdiphenyl guanidine, and “CBS” is the accelerantN-cyclohexyl-2-benzothiazolsulfenamide. F100 and F-115 were chosen asresins comparable in Tg with the modified thermoplastic resin.

TABLE 28 Reference Mixtures W1 to W7 and Inventive Compositions E1 andE2 W1 W2 W3 W4 W5 W6 W7 E1 E2 SSBR 100 100 100 100 100 100 100 100 100Silica 60 60 60 60 60 60 60 60 60 Kristalex ® F-85 0 20 40 0 0 0 0 0 0Kristalex ® F100 0 0 0 20 40 0 0 0 0 Kristalex ® F-115 0 0 0 0 0 20 40 00 Modified Kristalex ® 0 0 0 0 0 0 0 20 40 F-85 thermoplastic resin 6PPD2 2 2 2 2 2 2 2 2 Ozone wax 2 2 2 2 2 2 2 2 2 ZnO 2.5 2.5 2.5 2.5 2.52.5 2.5 2.5 2.5 Stearic acid 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 TESPD4.3 4.3 4.3 4.3 4.3 4.3 4.3 4.3 4.3 DPG 1 1 1 1 1 1 1 1 1 CBS 2 2 2 2 22 2 2 2 Sulfur 2 2 2 2 2 2 2 2 2 Physical Parameters Shore A hardness70.1 60.9 52.6 62.0 52.6 62 54.4 61.7 53.7 RT Shore A hardness 68.2 59.250.4 60.5 50.5 60.2 52.2 60.3 51.2 70° C. M300 (MPa) 5.6 7.7 5.2 8.0 5.28 5.9 8.0 5.4 Tensile strength 10.9 10.1 10.4 10.6 12.8 11.1 11.4 11.512.1 (MPa) Elongation at break 318 388 517 396 589 411 537 415 552 (%)Tan δ at 0° C. 0.173 0.265 0.468 0.288 0.527 0.301 0.493 0.285 0.544 Tanδ (max) at 55° C. 0.124 0.122 0.129 0.131 0.141 0.152 0.169 0.126 0.130Temp at Tan δ (max) −42 −30 −20 −30 −20 −30 −20 −29 −18 (° C.) Tg shift(° C.) n/a 12 22 12 22 12 22 13 24 Abrasion (mm³) 94 118 113 88 114 95134 102 120

Mixture production was performed under standard conditions in threestages in a laboratory tangential mixer. Test pieces were produced fromall of the mixtures by optimal vulcanization under pressure at 160° C.,and these test pieces were used to determine the material propertiestypical for the rubber industry. The following test methods were usedfor testing of the test pieces described above:

-   -   Shore A hardness (unit Shore A, abbreviated ShA) at room        temperature (RT) according to DIN 53 505;    -   Rebound elasticity (abbreviated as rebound) at room temperature        (RT) and 70° C. according to DIN 53 512;    -   Tension values at 50, 100 and 300% elongation (modulus 50,        modulus 100 or modulus 300) at room temperature (RT) according        to DIN 53 504;    -   Tensile strength and elongation at break at room temperature        according to DIN 53 504;    -   Wear at room temperature according to DIN53 516 or DIN/ISO 4649;        and    -   Glass transition temperature Tg of the rubber mixture from the        loss factor tan δ (tangent delta) by dynamic mechanical        measurement according to DIN 53 513 (temperature sweep).

Determination of the molecular weight (weight average Mw and numberaverage Mn) of the polymers is performed using gel permeationchromatography (GPC) with tetrahydrofuran (THF) as an eluent at 40° C.,calibrated with polystyrene-standard EasiCal PS-1 (Agilent, Santa Clara,Calif., US); size exclusion chromatography (SEC).

The loss factor “tan delta” (Tan δ) was determined in a dynamic-mechanictemperature sweep measurement according DIN 53513.

Tire performance tests were conducted on tires of size 205/55 R16 withthe respective tread compound mixtures indicated in Table 29. Rollingresistance measurements were performed according ISO 28580. Wet breakingwas measured as ABS-braking on wet asphalt with both a high and lowμ-value at an initial speed of 80 km/h. Dry braking was measured asABS-braking on dry asphalt with high μ-value at an initial speed of 100km/h. For snow performance, the snow traction for acceleration wasmeasured on a snow test track. The wear performance was evaluated by themass loss of the respective tires after 8800 km driving on roadcondition at an average temperature of 15° C. The rubber mixtures C1,C2, and E3 contained either non-modified or modified thermoplasticresins at 30 phr as shown in Table 29 (all values are in phr).

TABLE 29 Compound Mixtures for Tire Performance Tests C1 C2 E3 NaturalRubber 15 15 15 Synthetic rubber^(a) 85 85 85 Filler^(b) 128 128 128Kristalex ® F-85 30 0 0 Kristalex ® F-115 0 30 0 Modified Kristalex ®F-85 0 0 30 thermoplastic resin Softeners 25 25 25 Additives 14 14 14Silane^(c) 12 12 12 Vulcanization chemicals 5 5 5 ^(a): SSBR and BR^(b): CB and Silica ^(c): NXT (Momentive Performance Materials,Waterford, NY, US)

All values were measured in comparison to the reference mixture. Thereference values were normalized to 100%. The values that appear to besmaller than 100% represent a worsening of performance, whereas thevalues that appear to be greater than 100% characterize an improvementof performance.

Tire performance data is provided in Table 30, below.

TABLE 30 Tire Performance Results C1 C2 E3 RR 100 94 101 Wet 100 103 102Dry 100 101 100 Snow 100 96 100 Wear 100 92 100

These data can also be visualized by reference to FIG. 7, showing aspider diagram of the tire performance results of Kristalex® F-85 (C1),Kristalex® F-115 (C2), and the modified Kristalex® F-85 thermoplasticresin (E3).

As can be seen by the above data, selective removal the low molecularweight, low Tg oligomer content of the modified Kristalex® F-85thermoplastic resin creates a Tg that is higher; however, since the highmolecular weight fraction has not increased, thermoplastic resincompatibility with the elastomer is not compromised. This gives a betterbalance of wet grip and rolling resistance in tire tread applicationsbased on traditional viscoelastic predictors of these properties, asshown in the tire test results of Sample 3, i.e. comparison ofunmodified Kristalex® F-85 (sample C1) to modified Kristalex® F-85(sample E3), RR and wet. Additionally, the use of low oligomer contentthermoplastic resins in these applications results in similar compoundviscosity, vulcanization behavior, and physical properties compared totypical thermoplastic resins. Therefore, there is no apparent negativeimpact of the modified thermoplastic resin on these properties.

Further, comparison of the modified Kristalex® F-85 thermoplastic resinthat possesses an elevated Tg (Sample E3) as compared to the unmodifiedKristalex® F-85 thermoplastic resin, with a thermoplastic resin that hasa similar Tg, such as in unmodified Kristalex® F-115 (sample C2), showsthat increasing the Tg of thermoplastic resins by incorporating themodified thermoplastic resin into the tire tread yields superior snowperformance and wear properties and an apparent improvement in RR-wetbraking conflict, as shown by the results in Table 30.

All publications, patents and patent applications cited in thisspecification are herein incorporated by reference, and for any and allpurpose, as if each individual publication, patent or patent applicationwere specifically and individually indicated to be incorporated byreference. In the case of inconsistencies, the present disclosure willprevail.

The embodiments described hereinabove are further intended to explainbest modes known of practicing it and to enable others skilled in theart to utilize the disclosure in such, or other, embodiments and withthe various modifications required by the particular applications oruses. Accordingly, the description is not intended to limit it to theform disclosed herein. Also, it is intended that the appended claims beconstrued to include alternative embodiments.

What is claimed is:
 1. A modified thermoplastic resin prepared bypolymerization of one or more monomers, wherein the modifiedthermoplastic resin has a glass transition temperature (Tg) of between−50° C. and 160° C., wherein the modified thermoplastic resin has anumber average molecular weight of less than 3,000 g/mol, wherein themodified thermoplastic resin has a z-average molecular weight (Mz) ofless than 9,000 g/mol, wherein the modified thermoplastic resincomprises less than or equal to 55 wt % oligomers by gel permeationchromatography (GPC), or less than or equal to 38 wt % by highresolution thermogravimetric analysis (TGA), wherein oligomers consistof dimers, trimers, tetramers, pentamers, or a mixture thereof, of theone or more monomers, wherein the modified thermoplastic resin is a puremonomer thermoplastic (PMR) resin, a C5 thermoplastic resin, athermoplastic C5/C9 resin, a hydrogenated or partially hydrogenated C5resin and/or a hydrogenated or partially hydrogenated C5/C9thermoplastic resin, a C9 thermoplastic resin, a hydrogenated orpartially hydrogenated dicyclopentadiene (DCPD) thermoplastic resin, ahydrogenated or partially hydrogenated C9 thermoplastic resin, or ahydrogenated or partially hydrogenated PMR thermoplastic resin, or amixture thereof, wherein when the oligomer content is determined by GPC,then (a) when the modified thermoplastic resin is the PMR thermoplasticresin, then the value of Tg/Mz of the modified thermoplastic resin isgreater than or equal to 0.14 K/(g/mol), and the percent of the modifiedthermoplastic resin having a molecular weight of less than 300 g/mol isless than or equal to 2.5, and the percent of the modified thermoplasticresin having a molecular weight of less than 600 g/mol is less than orequal to 19; (b) when the modified thermoplastic resin is the C5thermoplastic resin, then the percent of the modified thermoplasticresin having a molecular weight of less than 300 g/mol is less than 3,and/or the percent of the modified thermoplastic resin having amolecular weight of less than 600 g/mol is less than 17; (c) when themodified thermoplastic resin is the C5/C9 thermoplastic resin, then thepercent of the modified thermoplastic resin having a molecular weight ofless than 300 g/mol is less than 3, and/or the percent of the modifiedthermoplastic resin having a molecular weight of less than 600 g/mol isless than 17; (d) when the modified thermoplastic resin is the C9thermoplastic resin, then the value of Tg/Mz of the modifiedthermoplastic resin is greater than 0.09 K/(g/mol), the percent of themodified thermoplastic resin having a molecular weight of less than 300g/mol is less than 5, and the percent of the modified thermoplasticresin having a molecular weight of less than 600 g/mol is less than 25;(e) when the modified thermoplastic resin is the hydrogenated orpartially hydrogenated DCPD thermoplastic resin, then the value of Tg/Mzof the modified thermoplastic resin is greater than 0.25 K/(g/mol), and:(i) the percent modified thermoplastic resin having a molecular weightof less than 300 g/mol is less than 16, and/or (ii) the percent modifiedthermoplastic resin having a molecular weight of less than 600 g/mol isless than 55; (f) when the modified thermoplastic resin is thehydrogenated or partially hydrogenated C5 thermoplastic resin and/or thehydrogenated or partially hydrogenated C5/C9 thermoplastic resin, thenthe percent modified thermoplastic resin having a molecular weight ofless than 300 g/mol is less than 15, and/or the percent modifiedthermoplastic resin having a molecular weight of less than 600 g/mol isless than 45; (g) the modified thermoplastic resin is the hydrogenatedor partially hydrogenated C9 thermoplastic resin, then the value ofTg/Mz of the modified thermoplastic resin is greater than or equal to0.19 K/(g/mol), the percent modified thermoplastic resin having amolecular weight of less than 300 g/mol is less than or equal to 10, andthe percent modified thermoplastic resin having a molecular weight ofless than 600 g/mol is less than 34; and (h) when the modifiedthermoplastic resin is the hydrogenated or the partially hydrogenatedPMR thermoplastic resin, and: the value of Tg/Mz of the modifiedthermoplastic resin is greater than or equal to 0.30 K/(g/mol), then thepercent modified thermoplastic resin having a molecular weight of lessthan 300 g/mol is less than 10, and/or the percent modifiedthermoplastic resin having a molecular weight of less than 600 g/mol isless than 45, or the value of Tg/Mz of the modified thermoplastic resinis less than 0.30 K/(g/mol), then the percent modified thermoplasticresin having a molecular weight of less than 300 g/mol is less than 10,and/or the percent modified thermoplastic resin having a molecularweight of less than 600 g/mol is less than 30, and wherein molecularweight of the modified thermoplastic resin is determined by gelpermeation chromatography (GPC) with polystyrene standards.
 2. Themodified thermoplastic resin of claim 1, wherein: the glass transitiontemperature (Tg) is between −50° C. and 160° C.; and/or the numberaverage molecular weight is less than 1,000 g/mol.
 3. The modifiedthermoplastic resin of claim 1, wherein: the Tg is between 0° C. and140° C.; the number average molecular weight is less than 850 g/mol;and/or the z-average molecular weight is less than 8,000 g/mol.
 4. Themodified thermoplastic resin of claim 1, wherein the modifiedthermoplastic resin has a glass transition temperature (Tg) of between0° C. and 140° C.
 5. The modified thermoplastic resin of claim 1,wherein the number average molecular weight (Mn) of the modifiedthermoplastic resin is less than or equal to 1,000 g/mol, and/or whereinthe z-average molecular weight (Mz) is less than or equal to 9,000g/mol.
 6. The modified thermoplastic resin of claim 1, wherein the highresolution TGA analysis is conducted with a thermal gravimetric analyzercalibrated by curie point of magnetic transition standards according toASTM method E1582, procedure C; and/or wherein the high resolution TGAanalysis is conducted using a TA Instruments Q500 thermal gravimetricanalyzer with sensitivity set to 2.0 and resolution set to 3.0 byheating the modified thermoplastic resin in nitrogen with a scanningrate of 20 degrees per minute from ambient temperature to 625° C.
 7. Themodified thermoplastic resin of claim 1, wherein GPC analysis isconducted at 30° C. in tetrahydrofuran solvent at a flow rate of 1ml/min with a GPC instrument comprising a refractive index detector, ahighly cross-linked polystyrene-divinylbenzene gel column, and/or acolumn comprising polymer particles with a nominal particle size of 6μm.
 8. A modified thermoplastic resin, wherein the modifiedthermoplastic resin possesses the properties of formula I:$\begin{matrix}{S = {\left( \frac{T_{g}}{M_{z}} \right){\text{/}\left\lbrack {{Oligomer} \times \left( {1 - \frac{T_{10}}{T_{\max}}} \right)} \right\rbrack}}} & I\end{matrix}$ wherein Tg is the glass transition temperature in degreesCelsius of the modified thermoplastic resin; wherein Mz is the z-averagemolecular weight of the modified thermoplastic resin; wherein Oligomeris the fraction of oligomer present in the modified thermoplastic resinas measured by high resolution thermal gravimetric analysis (TGA) or gelpermeation chromatography (GPC); wherein T₁₀ is the temperature at whichthe modified thermoplastic resin loses about 10% of its weight asmeasured by high resolution TGA; wherein T_(max) is the temperature ofthe maximum first derivative value of the modified thermoplastic resinas measured by high resolution TGA; wherein the modified thermoplasticresin is obtained by modification of pure monomer thermoplastic resin(PMR), C5 thermoplastic resin, C5/C9 thermoplastic resin, C9thermoplastic resin, dicyclopentadiene (DCPD) thermoplastic resin,hydrogenated or partially hydrogenated pure monomer (PMR) thermoplasticresin, hydrogenated or partially hydrogenated C5 thermoplastic resin,hydrogenated or partially hydrogenated C5/C9 thermoplastic resin,hydrogenated or partially hydrogenated C9 thermoplastic resin,hydrogenated or partially hydrogenated dicyclopentadiene (DCPD)thermoplastic resin, or a mixture thereof, and wherein when the oligomercontent is determined by TGA, then (a) when the modified thermoplasticresin is the PMR thermoplastic resin and the value of Tg/Mz is greaterthan or equal to 0.14 K/(g/mol), then Oligomer is less than 0.17, and/orthe value of T₁₀/T_(max) is greater than or equal to 0.90, and/or thevalue of S is greater than 12; (b) when the modified thermoplastic resinis the C5 thermoplastic resin, then Oligomer is less than 0.14, and/orthe value of T₁₀/T_(max) is greater than or equal to 0.92, and/or thevalue of S is greater than or equal to 5; (c) when the modifiedthermoplastic resin is the C5/C9 thermoplastic resin, then Oligomer isless than 0.15, and/or the value of T₁₀/T_(max) is greater than or equalto 0.92, and/or the value of S is greater than or equal to 10; (d) whenthe modified thermoplastic resin is the C9 thermoplastic resin and thevalue of Tg/Mz is greater than or equal to 0.12 K/(g/mol), then Oligomeris less than or equal to 0.15, and/or the value of T₁₀/T_(max) isgreater than or equal to 0.88, and/or the value of S is greater than orequal to 16; (e) when the modified thermoplastic resin is thehydrogenated or partially hydrogenated DCPD thermoplastic resin and thevalue of Tg/Mz is greater than 0.25 K/(g/mol), then Oligomer is lessthan 0.31, and/or the value of T₁₀/T_(max) is greater than 0.85, and/orthe value of S is greater than or equal to 10; (f) when the modifiedthermoplastic resin is the hydrogenated or partially hydrogenated PMRthermoplastic resin and the value of Tg/Mz is greater than or equal to0.30 K/(g/mol), then Oligomer is less than or equal to 0.16, and/or thevalue of T₁₀/T_(max) is greater than 0.85, and/or the value of S isgreater than or equal to 22; (g) when the modified thermoplastic resinis the hydrogenated or partially hydrogenated PMR thermoplastic resinand the value of Tg/Mz is less than 0.30 K/(g/mol), then Oligomer isless than 0.38, and/or the value of T₁₀/T_(max) is greater than 0.75,and/or the value of S is greater than or equal to 5; (h) when themodified thermoplastic resin is the hydrogenated or partiallyhydrogenated C5 thermoplastic resin or the hydrogenated or partiallyhydrogenated C5/C9 thermoplastic resin, then Oligomer is less than 0.30,and/or the value of T₁₀/T_(max) is greater than or equal to 0.90, and/orthe value of S is greater than or equal to 10; or (i) when the modifiedthermoplastic resin is the hydrogenated or partially hydrogenated C9thermoplastic resin and the value of Tg/Mz is greater than or equal to0.19 K/(g/mol), then Oligomer is less than 0.13, and/or the value ofT₁₀/T_(max) is greater than or equal to 0.90, and/or the value of S isgreater than or equal to
 16. 9. The modified thermoplastic resin ofclaim 8, wherein: the glass transition temperature (Tg) is between −50°C. and 160° C.; the number average molecular weight is less than 1,000g/mol; and/or the z-average molecular weight is less than 9,500 g/mol.10. The modified thermoplastic resin of claim 8, wherein: the Tg isbetween 0° C. and 140° C.; the number average molecular weight is lessthan 850 g/mol; and/or the z-average molecular weight is less than 8,000g/mol.
 11. The modified thermoplastic resin of claim 8, wherein theoligomer content is determined by GPC, and wherein: (aa) when themodified thermoplastic resin is a PMR resin, then the value of Tg/Mz isgreater than or equal to 0.14 K/(g/mol), the Oligomer having a molecularweight of less than 300 g/mol is less than or equal to 0.03, and theOligomer having a molecular weight of less than 600 g/mol is less thanor equal to 0.2; (bb) when the modified thermoplastic resin is a C5resin, then: the Oligomer having a molecular weight of less than 300g/mol is less than 0.03, and/or the Oligomer having a molecular weightof less than 600 g/mol is less than 0.17; (cc) when the modifiedthermoplastic resin is a C5/C9 resin, then: the Oligomer having amolecular weight of less than 300 g/mol is less than 0.03, and/or theOligomer having a molecular weight of less than 600 g/mol is less than0.17; (dd) when the modified thermoplastic resin is a C9 resin, then thevalue of Tg/Mz is greater than 0.09 K/(g/mol), the Oligomer having amolecular weight of less than 300 g/mol is less than 0.05, and theOligomer having a molecular weight of less than 600 g/mol is less than0.25; (ee) when the modified thermoplastic resin is a hydrogenated orpartially hydrogenated DCPD resin, then the value of Tg/Mz is greaterthan 0.25 K/(g/mol), and wherein: the Oligomer having a molecular weightof less than 300 g/mol is less than 0.16, and/or the Oligomer having amolecular weight of less than 600 g/mol is less than 0.55; (ff) when themodified thermoplastic resin is a hydrogenated or partially hydrogenatedC5 resin and/or a hydrogenated or partially hydrogenated C5/C9 resin,then: the Oligomer having a molecular weight of less than 300 g/mol isless than 0.15, and/or the Oligomer having a molecular weight of lessthan 600 g/mol is less than 0.45; (gg) when the modified thermoplasticresin is hydrogenated or partially hydrogenated C9 resin, the value ofTg/Mz is greater than or equal to 0.19 K/(g/mol), then: the Oligomerhaving a molecular weight of less than 300 g/mol is less than or equalto 0.10, and the Oligomer having a molecular weight of less than 600g/mol is less than 0.34; or (hh) when the modified thermoplastic resinis a hydrogenated or partially hydrogenated PMR resin, then: the valueof Tg/Mz is greater than or equal to 0.30 K/(g/mol), the Oligomer havinga molecular weight of less than 300 g/mol is less than 0.10, and/or theOligomer having a molecular weight of less than 600 g/mol is less than0.45, or the value of Tg/Mz is less than 0.30 K/(g/mol), the Oligomerhaving a molecular weight of less than 300 g/mol is less than 0.10,and/or the Oligomer having a molecular weight of less than 600 g/mol isless than 0.30.
 12. The modified thermoplastic resin of claim 8, whereinthe modified thermoplastic resin is a PMR resin and/or a modifiedhydrogenated or partially hydrogenated PMR resin, and wherein forOligomer having a molecular weight of less than 300 g/mol, S is greaterthan
 2000. 13. The modified thermoplastic resin of claim 8, wherein themodified thermoplastic resin is a hydrogenated or partially hydrogenatedC9 resin, and wherein for Oligomer having a molecular weight of lessthan 300 g/mol, S is greater than
 90. 14. The modified thermoplasticresin of claim 8, wherein the modified thermoplastic resin has a glasstransition temperature (Tg) of between −50° C. and 160° C., between 0°C. and 140° C., or between 20° C. and 120° C.
 15. The modifiedthermoplastic resin of claim 8, wherein the number average molecularweight (Mn) of the modified thermoplastic resin is less than or equal to1,000 g/mol, 500 g/mol, or 250 g/mol, and/or wherein the z-averagemolecular weight (Mz) is less than or equal to 9,000 g/mol, 8,000 g/mol,or 6,000 g/mol.
 16. The modified thermoplastic resin of claim 8, whereinthe oligomer content is determined by GPC, and wherein: (aaa) when themodified thermoplastic resin is a PMR resin, then: for Oligomer having amolecular weight of less than 600 g/mol, S is greater than 14, and/orfor Oligomer having a molecular weight of less than 300 g/mol, S isgreater than 67; (bbb) when the modified thermoplastic resin is a C5resin, then: for Oligomer having a molecular weight of less than 600g/mol, S is greater than 8, and/or for Oligomer having a molecularweight of less than 300 g/mol, S is greater than 36; (ccc) when themodified thermoplastic resin is a C5/C9 resin, then: for Oligomer havinga molecular weight of less than 600 g/mol, S is greater than 8, and/orfor Oligomer having a molecular weight of less than 300 g/mol, S isgreater than 36; (ddd) when the modified thermoplastic resin is a C9resin, the value of Tg/Mz is greater than 0.09 K/(g/mol), then: forOligomer having a molecular weight of less than 600 g/mol, S is greaterthan 8, and/or for Oligomer having a molecular weight of less than 300g/mol, S is greater than 38; (eee) when the modified thermoplastic resinis a hydrogenated or partially hydrogenated DCPD resin, then: forOligomer having a molecular weight of less than 600 g/mol, S is greaterthan 5, or for Oligomer having a molecular weight of less than 300g/mol, S is greater than 17; (fff) when the modified thermoplastic resinis a hydrogenated or partially hydrogenated C5 resin and/or ahydrogenated or partially hydrogenated C5/C9 resin, then: for Oligomerhaving a molecular weight of less than 600 g/mol, S is greater than 5,and/or for Oligomer having a molecular weight of less than 300 g/mol, Sis greater than 10; (ggg) when the modified thermoplastic resin ishydrogenated or partially hydrogenated C9 resin, the value of Tg/Mz isgreater than or equal to 0.19 K/(g/mol), then: for Oligomer having amolecular weight of less than 600 g/mol, S is greater than 6, and/or forOligomer having a molecular weight of less than 300 g/mol, S is greaterthan 29; or (hhh) when the modified thermoplastic resin is ahydrogenated or partially hydrogenated PMR resin, and: (A) the value ofTg/Mz is greater than or equal to 0.30 K/(g/mol), then, for Oligomerhaving a molecular weight of less than 600 g/mol, S is greater than 8,and/or for Oligomer having a molecular weight of less than 300 g/mol, Sis greater than 26; or (B) the value of Tg/Mz is less than 0.30K/(g/mol), then, for Oligomer having a molecular weight of less than 600g/mol, S is greater than 2, and/or for Oligomer having a molecularweight of less than 300 g/mol, S is greater than
 5. 17. The modifiedthermoplastic resin of claim 8, wherein: the high resolution TGAanalysis is conducted using a thermal gravimetric analyzer calibrated bycurie point of magnetic transition standards according to ASTM methodE1582, procedure C; and/or wherein the high resolution TGA analysis isconducted using a TA Instruments Q500 thermal gravimetric analyzer withsensitivity set to 2.0 and resolution set to 3.0 by heating the modifiedthermoplastic resin in nitrogen with a scanning rate of 20 degrees perminute from ambient temperature to 625° C., and/or the GPC analysis isconducted at 30° C. in tetrahydrofuran solvent at a flow rate of 1ml/min with a GPC instrument comprising a refractive index detector, ahighly cross-linked polystyrene-divinylbenzene gel column, and/or acolumn comprising polymer particles with a nominal particle size of 6μm.